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Palladium absorbs large volumetric quantities of hydrogen at room temperature and ambient pressure, making the palladium hydride system a promising candidate for hydrogen storage. Here, we use Bragg coherent diffraction imaging to map the strain associated with defects in three dimensions before and during the hydride phase transformation of an individual octahedral palladium nanoparticle, synthesized using a seed-mediated approach. The displacement distribution imaging unveils the location of the seed nanoparticle in the final nanocrystal. By comparing our experimental results with a finite-element model, we verify that the seed nanoparticle causes a characteristic displacement distribution of the larger nanocrystal. During the hydrogen exposure, the hydride phase is predominantly formed on one tip of the octahedra, where there is a high number of lower coordinated Pd atoms. Our experimental and theoretical results provide an unambiguous method for future structure optimization of seed-mediated nanoparticle growth and in the design of palladium-based hydrogen storage systems. Palladium can absorb high volumes of hydrogen, but the morphology and 3D displacements occurring during palladium hydride phase formation are not fully characterized in the literature. Here, the authors use Bragg coherent diffraction imaging to map the strain within an individual palladium nanoparticle before and during hydride phase transformation, identifying a characteristic displacement caused by the seed particle in the nanocrystal.

Copper is an earth-abundant element that can be used to reduce the high cost and unsatisfactory durability of pure Pt catalysts by the formation of bimetallic Pt–M nanocrystals. Among CuPt nanostru...

Advances in new systems of organic–inorganic hybrid nanocomposites are less prevalent, owing to a lack of facile strategies for precise control of their structures, compositions, and, hence, their properties. In this work, Au-BINOL hybrid nanocomposites with eccentric and concentric nanostructures were produced. The hybrid nanocomposites containing two distinct moieties of inorganic Au nanocrystals and organic BINOL nanospheres were applied to the catalytic hydrogenation of 4-nitrophenol with NaBH4 in the aqueous phase with and without the illumination of visible light. Here, we demonstrate that the existence of Au–BINOL interfaces offers benefits to their performance. The eccentric nanostructures made with CTAC show the superior activity from large Au–BINOL interfaces formed between the BINOL nanospheres and the faces of Au nanoplates. They further exhibit a high Au localized surface plasmon resonance (LSPR)-enhancement effect on the photoreduction of 4-nitrophenol, which is attributed to the strong LSPR...

The combined functionality of components in organic–inorganic hybrid nanomaterials render them efficient nanoreactors. However, the development in this field is limited due to a lack of synthetic avenues and systematic control of the growth kinetics of hybrid structures. In this work, we take advantage of an ionic switch for regio-control of Au-BINOL(1,1′-Bi-2-naphthol) hybrid nanostructures. Aromatic BINOL molecules assemble into nanospheres, concomitant with the growth of the Au nanocrystals. The morphological evolution of Au nanocrystals is solely controlled by the presence of halides in the synthetic system. Here we show that quaternary ammonium surfactants (CTAB or CTAC), not only bridging Au and BINOL, but also contributing to the formation of concentric or eccentric structures when their concentrations are tuned to the range of 10–5 to 10–3 M. This facile strategy offers the potential advantage of scalable production, with diverse functional organic–inorganic hybrid nanocomposites being produced ba...

Control of morphology in the synthesis of Rh nanocrystals can be used to precisely tailor the electronic surface structure; this in turn directly influences their performance in catalysis applications. Many works bring attention to the development of Rh nanostructures with low-index surfaces, but limited effort has been placed on the study of high-index and surface-defect-enriched nanocrystals as they are not favored by thermodynamics due to the involvement of high-energy surfaces and increased surface-to-volume ratios. In this work, we demonstrate an aqueous synthesis of concave Rh nanotetrahedra (CTDs) serving as efficient catalysts for energy conversion reactions. CTDs are surface-defect-rich structures that form through a slow growth rate and follow the four-step model of metallic nanoparticle growth. By tuning the surfactant concentration, the morphology of Rh CTDs evolved into highly excavated nanotetrahedra (HETDs) and twinned nanoparticles (TWs). Unlike the CTD surfaces with abundant adatoms and v...

Platinum was coated on the surfaces of copper nanocubes to form Cu–CuPt core–alloy–frame nanocrystals with a rhombic dodecahedral (RD) shape. Co-reduction of Pt2+ ions and residual Cu+ ions in the supernatant of the Cu nanocube solution followed by the interdiffusion of Cu and Pt atoms over the core–shell interface allowed their formation. Growth in the ⟨100⟩ directions of the {100}-terminated Cu nanocubes resulted in the {110}-faceted rhombic dodecahedra. By the introduction of additional Pt precursor, the {100} vertices of the Cu–CuPt RD nanocrystals could be selectively extended to form spiny CuPt RD nanocrystals. After removing the Cu core template, both CuPt alloy RD and spiny CuPt alloy RD nanoframes (NFs) were obtained with Pt/Cu ratios of 26/74 and 41/59, respectively. Abundant surface defects render them highly active catalysts due to the open frame structure of both sets of NFs. The spiny RD NFs showed superior specific activity toward the oxygen reduction reaction, 1.3 and 3 times to those of t...

Au-Pd nanocrystals are an intriguing system to study the integrated functions of localized surface plasmon resonance (LSPR) and heterogeneous catalysis. Gold is both durable and can harness incident light energy to enhance the catalytic activity of another metal, such as Pd, via the SPR effect in bimetallic nanocrystals. Despite the superior catalytic performance of icosahedral (IH) nanocrystals compared to alternate morphologies, the controlled synthesis of alloy and core-shell IH is still greatly challenged by the disparate reduction rates of metal precursors and lack of continuous epigrowth on multiply twinned boundaries of such surfaces. Herein, we demonstrate a one-step strategy for the controlled growth of monodisperse Au-Pd alloy and core-shell IH with terraced shells by turning an ionic switch between [Br(-)]/[Cl(-)] in the coreduction process. The core-shell IH nanocrystals contain AuPd alloy cores and ultrathin Pd shells (2 nm). They not only display more than double the activity of the commercial Pd catalysts in ethanol electrooxidation attributed to monatomic step terraces but also show SPR-enhanced conversion of 4-nitrophenol. This strategy holds promise toward the development of alternate bimetallic IH nanocrystals for electrochemical and plasmon-enhanced catalysis.

Geometric modification of Au nanostructures is typically achieved in multistep reactions, where synthesis parameters need to be well-controlled. In this work, we report a facile method using IrCl3 to refine morphologically diverse Au nanostructures and trigger their morphological transformations. The synthesis is accomplished at room temperature by an iterative process of galvanic dissolution and recursive growth. Seeds retrieved after the dissolution of different Au nanostructure archetypes served in the structural recovery and morphological transformation via rapid and slow regrowth, respectively. The rapid regrowth was accomplished by adding ascorbic acid (AA), while the slow regrowth occurred spontaneously. In the structural recovery, the nanostructures regrew back to their original morphologies. Improvements in the shape quality and size distributions were observed for the rapid regrowth case. In the spontaneous slow regrowth transformation, the resulting nanostructures were encased by {111} facets, ...

Cubic and octahedral Cu2O nanocrystals and Au–Cu2O core–shell heterostructures are used as sacrificial templates for the growth of Cu2S nanocages and Au–Cu2S core–cage structures. A rapid sulfidation process involving a surface reaction of Cu2O nanocrystals with Na2S, followed by etching of the Cu2O cores with HCl solution for ≈5 sec, results in the fabrication of Cu2S cages with a wall thickness of 10–20 nm. Transmission electron microscopy characterization reveals the formation of crystalline walls and the presence of ultrasmall pores with sizes of 1 nm or less. Formation of Cu2O–Cu2S core–shell structures and their conversion into Cu2S cages is verified by UV–vis absorption spectroscopy. X-ray photoelectron spectra further confirm the composition of the cages as Cu2S. The entire hollowing process via the Kirkendall effect is recorded using in-situ transmission X-ray microscopy. After shell formation, continuous ionic diffusion removes the interior Cu2O. Intermediate structures with remaining central Cu2O portions and bridging arms to the surrounding cages are observed. The nanocages are also shown to allow molecular transport: anthracene and pyrene penetration into the cages leads to enhanced fluorescence quenching immediately upon adsorption onto the surfaces of the encapsulated gold nanocrystals.

We report highly facet-dependent electrical properties of Cu(2)O nanocubes and octahedra and significant enhancement of gold nanocrystal cores to the electrical conductivity of Au-Cu(2)O core-shell octahedra. Cu(2)O nanocubes and octahedra and Au-Cu(2)O core-shell cubes and octahedra were synthesized by following our reported facile procedures at room temperature. Two oxide-free tungsten probes attached to a nanomanipulator installed inside a scanning electron microscope made contacts to a single Cu(2)O nanocrystal for the I-V measurements. Pristine Cu(2)O octahedra bounded by {111} facets are 1100 times more conductive than pristine Cu(2)O cubes enclosed by {100} faces, which are barely conductive. Core-shell cubes are only slightly more conductive than pristine cubes. A 10,000-fold increase in conductivity over a cube has been recorded for an octahedron. Remarkably, core-shell octahedra are far more conductive than pristine octahedra. The same facet-dependent electrical behavior can still be observed on a single nanocrystal exposing both {111} and {100} facets. This new fundamental property may be observable in other semiconductor nanocrystals. We also have shown that both core-shell cubes and octahedra outperform pristine cubes and octahedra in the photodegradation of methyl orange. Efficient photoinduced charge separation is attributed to this enhanced photocatalytic activity. Interestingly, facet-selective etching occurred over the {100} corners of some octahedra and core-shell octahedra during photocatalysis. The successful preparation of Au-Cu(2)O core-shell heterostructures with precise shape control has offered opportunities to discover new and exciting physical and chemical properties of nanocrystals.

Summary The ability to prepare inorganic nanocrystals with well-defined morphologies and sharp faces should facilitate the examination of their facet-dependent surface, catalytic, electrical, and other properties. In this review we cover different synthetic methods for the growth of Cu 2 O nanocrystals with morphological control. Cu 2 O nanocrystals with cubic, cuboctahedral, truncated octahedral, octahedral, and multipod structures have been prepared mainly by wet chemical, electrodeposition, and solvothermal synthesis methods. Methods used for the formation of hollow Cu 2 O nanocubes, octahedra, and truncated rhombic dodecahedra are also presented. Morphology of Cu 2 O nanocrystals can be expanded with the use of gold nanocrystal cores to guide the overgrowth of Cu 2 O shells. Surface properties of Cu 2 O nano- and microcrystals with sharp faces have been examined in a few studies. The {1 1 1} faces were found to interact well with negatively charged molecules, while the {1 0 0} faces are less sensitive to molecular charges. Preferential adsorption of sodium dodecyl sulfate molecules on the {1 1 1} faces of Cu 2 O crystals has been demonstrated via plane-selective deposition of gold nanoparticles on only the {1 0 0} faces. It is expected that the development of improved synthetic methods for Cu 2 O nanocrystals and more knowledge of their facet-dependent properties should lead to their applications in photoactivated energy conversion and catalysis.

We report the growth of core−shell Ga−GaN nanostructures by simple refluxing of a mixture of GaCl3 and lithium bis(trimethylsilyl)amide (LiHMDS) in trioctylamine at 380 °C for 24 h under nitrogen flow. The resulting spherical Ga−GaN nanostructures had diameters of ∼550 nm. By immersing the nanostructures in aqua regia, the gallium cores could be removed, and hollow GaN spheres with thicknesses of 15−25 nm were produced. The shells consisted of connected GaN nanocrystals of both cubic and hexagonal phases. Infrared spectroscopy confirmed the presence of silica or silicate in the GaN shells. The silicon source likely comes from the pyrolysis of LiHMDS. The growth process was studied by examining the intermediate products formed. Gallium metal cores appeared below 380 °C, followed by the slow formation of GaN nanocrystals on the core surfaces. The slow growth of the GaN shells is related to the gradual supply of the nitrogen source from the thermal decomposition of LiHMDS. Thinner shells with a thickness of ...

Here we report the hydrothermal synthesis of octahedral gold nanocrystals from an aqueous solution of HAuCl4, trisodium citrate, and cetyltrimethylammonium bromide (CTAB) surfactant. By heating the mixture at 110 °C for 6, 12, 24, 48, and 72 h, gold octahedra with approximate average sizes of 30, 60, 90, 120, and 150 nm can be obtained. The percent yield of octahedral nanocrystals is more than 90% for all the samples. Products formed at shorter reaction times were also examined. Structural characterization confirmed that the octahedra are bounded by entirely {111} faces. As particle size increases, the surface plasmon resonance (SPR) absorption band red-shifts from 543 to 635 nm. These monodisperse gold octahedra can spontaneously self-assemble into long-range ordered packing structures upon water evaporation. Three types of self-assembled structures with faces, edges, or corners of the octahedra contacting the substrates have been identified. Particle size can affect the type of packing structure they ad...

We report a facile method for the synthesis of cuprous oxide nanocrystals with systematic shape evolution. Monodisperse truncated cubic, cuboctahedral, truncated octahedral, and octahedral nanocrystals can be synthesized directly in an aqueous solution of CuCl2, sodium dodecyl sulfate (SDS) surfactant, hydroxylamine (NH2OH·HCl) reductant, and NaOH by simply varying the volume of hydroxylamine added to the reaction mixture. SDS surfactant was found to be necessary for a precise control of the nanocrystal morphology. Adjustment of the volume of NaOH added provides a means to vary the particle size. In the case of octahedral nanocrystals, particles with sizes of 160−460 nm can be prepared. By examining the intermediate products formed, which resemble the final nanocrystal structures, a growth mechanism is proposed. Optical characterization of these Cu2O nanocrystals showed band gap absorption at 470−490 nm and strong light scattering bands extending from the visible to the near-infrared light region. All fou...

We report the high yield growth of monodispersed Cu 2 O nanocubes with approximate average sizes of 40, 65, 100, 230, and 420 nm using a seed-mediated synthesis approach in aqueous solution. The nanocubes are formed in 2 hours at room temperature. The standard deviation of the nanocube sizes in each sample is below 10 %. Structural analysis revealed that these nanocubes have six {100} faces, and possess truncated {110} edges and {111} corners. The combination of sodium dodecyl sulfate (SDS) and CuSO 4 was found to be critical to the formation of structurally well-defined Cu 2 O nanocubes. The nanocubes presumably were formed through the controlled aggregation of Cu 2 O seed particles and then surface reconstruction under the influence of SDS capping surfactant and sulfate ions to yield this truncated cubic structure. Optical characterization showed that nanocubes smaller than 100 nm absorb at -490 nm, while nanocubes larger than 200 nm display an absorption band at 515-525 nm. Additional absorption feature was observed in the red and near-infrared regions for the larger Cu 2 O nanocubes due to the light scattering effect. The investigation of the application of these nanocubes for the photodegradation of rhodamine B revealed the {111} crystal surfaces as the active surfaces responsible for the photocatalytic activity of Cu 2 O nanostructures. This simple and rapid synthesis of monodispersed Cu 2 O nanocubes should allow further examination of their various properties as a function of nanocrystal sizes.

The effect of lattice strain on the catalytic properties of Pd nanoparticles is systematically studied. Synthetic strategies for the preparation of a series of shape-controlled Pd nanocrystals with lattice strain generated from different sources has been developed. All of these nanocrystals were created with the same capping agent under similar reaction conditions. First, a series of Pd nanoparticles was synthesized that were enclosed in {111} surfaces: Single-crystalline Pd octahedra, single-crystalline AuPd core–shell octahedra, and twinned Pd icosahedra. Next, various {100}-terminated particles were synthesized: Single-crystalline Pd cubes and single-crystalline AuPd core–shell cubes. Different extents of lattice strain were evident by comparing the X-ray diffraction patterns of these particles. During electrocatalysis, decreased potentials for CO stripping and increased current densities for formic-acid oxidation were observed for the strained nanoparticles. In the gas-phase hydrogenation of ethylene, the activities of the strained nanoparticles were lower than those of the single-crystalline Pd nanoparticles, perhaps owing to a larger amount of cetyl trimethylammonium bromide on the surface.

A general synthetic strategy for yolk-shell nanocrystal@ZIF-8 nanostructures has been developed. The yolk-shell nanostructures possess the functions of nanoparticle cores, microporous shells, and a cavity in between, which offer great potential in heterogeneous catalysis. The synthetic strategy involved first coating the nanocrystal cores with a layer of Cu(2)O as the sacrificial template and then a layer of polycrystalline ZIF-8. The clean Cu(2)O surface assists in the formation of the ZIF-8 coating layer and is etched off spontaneously and simultaneously during this process. The yolk-shell nanostructures were characterized by transmission electron microscopy, scanning electron microscopy, X-ray diffraction, and nitrogen adsorption. To study the catalytic behavior, hydrogenations of ethylene, cyclohexene, and cyclooctene as model reactions were carried out over the Pd@ZIF-8 catalysts. The microporous ZIF-8 shell provides excellent molecular-size selectivity. The results show high activity for the ethylene and cyclohexene hydrogenations but not in the cyclooctene hydrogenation. Different activation energies for cyclohexene hydrogenation were obtained for nanostructures with and without the cavity in between the core and the shell. This demonstrates the importance of controlling the cavity because of its influence on the catalysis.

We report a seed-mediated synthesis method for the preparation of gold nanocrystals with systematic shape evolution from truncated cubic to cubic, trisoctahedral, and rhombic dodecahedral structures in aqueous solution for the first time. Nanocrystals with transitional morphologies were also synthesized. The combination of using cetyltrimethylammonium chloride (CTAC) surfactant and a very small amount of NaBr to control the bromide concentration in the growth solution was found to be critical to the formation of nanocubes. Variation in the volume of ascorbic acid added to the growth solution enabled the fine control of nanocrystal morphology. Nanocubes and rhombic dodecahedra with controlled sizes of 30-75 nm were prepared by adjusting the volume of the seed solution added to the growth solution. They can self-assemble into ordered packing structures on substrates because of their uniform sizes. XRD, TEM, and UV-vis absorption characterization of the different products synthesized have been performed. By increasing the bromide concentration 5-fold that used to make the nanocubes, unusual right bipyramids of gold bounded by six {100} faces were produced. The high product purity and excellent size control of this facile synthetic approach should make these novel gold nanostructures be readily available for a wide range of studies.

Synthesis of branched gold nanocrystals by a seeding growth approach is described. In this process, HAuCl4 aqueous solution was supplied stepwise to grow the gold seeds (approximately 2.5 nm) into larger nanoparticles with a highly faceted particle structure (approximately 15-20 nm in diameter). Sodium dodecyl sulfate (SDS) served as a capping agent to facilitate the formation of highly faceted nanoparticles, and ascorbic acid was used as a weak reducing agent. The highly faceted nanoparticles then transformed into branched nanocrystals (approximately 40 nm in length) by further addition of the SDS-HAuCl4 solution and ascorbic acid for particle growth. The branched nanocrystals show bipod, tripod, tetrapod, and pentapod structures and are composed of mainly (111) lattice planes. These multipods appear to grow along the twin boundaries of the initially formed highly faceted gold nanoparticles, as the twin boundaries on the pods originate from the centers of the branched nanocrystals. The concentration of ascorbate ions in the solution was found to have a profound influence on branch formation. These branched nanocrystals are stable to storage at low temperature (that is, 4 degrees C), but they may slowly evolve into a multitwinned faceted crystal structure (that is, pentagonal-shaped decahedral structure) when stored at 30 degrees C.