Nm In Edge Length Research Articles

Continuous and Scalable Production of Platinum Nanocubes with Uniform and Controllable Sizes in Air-Free Droplet Reactors.

Platinum (Pt) nanocrystals hold the key to a variety of catalytic applications, and those with a cubic shape are attractive as a reference catalyst due to their well-defined {100} facets on the surface. Here we demonstrate the use of droplet reactors as a viable platform for the continuous and scalable production of Pt nanocubes with uniform and controllable sizes. The synthesis was found to be sensitive to the O2 from air because of the oxidative etching associated with the O2/Br- pair. As such, either silicone oil or an inert gas had to be employed as the carrier phase to keep the droplets isolated from air. By controlling the amounts of the precursor and halide ions, the edge length of the Pt nanocubes could be tuned from 5-7 nm. In the setting of a millifluidic device, the droplet reactors could be used to achieve a production rate as high as 31.8 mg min-1, about 10-100 times greater than what has been reported in the literature. We also evaluated the electrocatalytic properties of the as-obtained Pt nanocubes toward the oxygen reduction reaction (ORR) and methanol oxidation reaction (MOR). For the Pt nanocubes of 6 nm in edge length, they showed a specific activity of 0.27 mA cm-2 toward ORR at 0.9 V and a specific activity of 0.96 mA cm-2 toward MOR at the anodic potential.

Hydrothermal synthesis of Zn-doped α-Fe2O3 nanocubes for selective detection of triethylamine

With the growing attention on environment protection, gas sensors fabricated with metal oxide semiconductor (MOS) have stimulated increasing research interest because of their capability for fast detection of various harmful gases. Here, Zn-doped α-Fe2O3 nanocubes (ZFO NCs) with about 300–500 nm in edge length were successfully prepared via a surfactant-free hydrothermal route and their gas sensing properties were investigated by using as bare α-Fe2O3 NCs as reference. It was found that as applied as active materials for detecting volatile organic compounds (VOCs), the obtained ZFO NCs showed some impressively improved triethylamine (TEA) sensing performances, especially of better selectivity and higher sensitivity. The response (Ra/Rg) of the best ZFO sensor (ZFO-5) to 100 ppm TEA was as high as 64.3, and its selectivity coefficient (STEA/Ammonia) was 6.50, both of which were well above that of the pure α-Fe2O3 sensor. Besides, the ZFO-5 sensor also shows good stability and repeatability. The gas sensitive mechanism of the ZFO NCs was discussed.

Hydrothermal Synthesis of Iridium-Substituted NaTaO3 Perovskites.

Iridium-containing NaTaO3 is produced using a one-step hydrothermal crystallisation from Ta2O5 and IrCl3 in an aqueous solution of 10 M NaOH in 40 vol% H2O2 heated at 240 °C. Although a nominal replacement of 50% of Ta by Ir was attempted, the amount of Ir included in the perovskite oxide was only up to 15 mol%. The materials are formed as crystalline powders comprising cube-shaped crystallites around 100 nm in edge length, as seen by scanning transmission electron microscopy. Energy dispersive X-ray mapping shows an even dispersion of Ir through the crystallites. Profile fitting of powder X-ray diffraction (XRD) shows expanded unit cell volumes (orthorhombic space group Pbnm) compared to the parent NaTaO3, while XANES spectroscopy at the Ir LIII-edge reveals that the highest Ir-content materials contain Ir4+. The inclusion of Ir4+ into the perovskite by replacement of Ta5+ implies the presence of charge-balancing defects and upon heat treatment the iridium is extruded from the perovskite at around 600 °C in air, with the presence of metallic iridium seen by in situ powder XRD. The highest Ir-content material was loaded with Pt and examined for photocatalytic evolution of H2 from aqueous methanol. Compared to the parent NaTaO3, the Ir-substituted material shows a more than ten-fold enhancement of hydrogen yield with a significant proportion ascribed to visible light absorption.

Quantifying Electrocatalytic Reduction of CO2 on Twin Boundaries

Summary A protocol relying on the use of silver nanostructures with well-defined dimensions and morphologies (e.g., nanocubes and nanowires) has been developed to differentiate and quantitatively determine the atom-specific activities of different surface atoms toward catalyzing electrochemical CO2 reduction reaction (CO2RR). The atom-specific activity of the twin-boundary edges (TBEs) is comparable to (or slightly higher than) that of the single-crystal edges (SCEs) formed from the crossing of two {100} surfaces, and it is on the order of ∼16 attoampere/atom (aA/atom) toward electrochemical CO2RR. This value is more than two orders higher than the atom-specific activity of the {100} surface atoms, i.e., ∼0.1 aA/atom. The high catalytic activity of the TBEs, which represent a class of commonly existing surface defects in stable metal nanostructures with face-centered cubic lattices, is consistent with the DFT calculations, in which the bridge-type binding configuration of COOH∗ at the TBEs stabilizes this intermediate to promote overall CO2RR.

Copper Nanocubes for CO2 Reduction in Gas Diffusion Electrodes.

Electroreduction of CO2 represents a promising solution for addressing the global challenges in energy and sustainability. This reaction is highly sensitive to the surface structure of electrocatalysts and the local electrochemical environment. We have investigated the effect of Cu nanoparticle shape on the electrocatalysis of CO2 reduction by using gas-diffusion electrodes (GDEs) and flowing alkaline catholytes. Cu nanocubes of ∼70 nm in edge length are synthesized with {100} facets preferentially exposed on the surface. They are demonstrated to possess substantially enhanced catalytic activity and selectivity for CO2 reduction, compared to Cu nanospheres of similar particle sizes. The electrocatalytic performance was further found to be dependent on the concentration of electrolyte (KOH). The Cu nanocubes reach a Faradaic efficiency of 60% and a partial current density of 144 mA/cm2 toward ethylene (C2H4) production, with the catalytic enhancement being attributable to a combination of surface structure and electrolyte alkalinity effects.

Wüstite-type Fe0.78Mn0.22O nanocubes: A new class for high-sensitive T2-weighted magnetic resonance imaging agent

Wüstite-type Fe0.78Mn0.22O nanocubes, with a uniform size of ∼10 nm in edge length, have been synthesized by thermal-decomposition approach. The nanocubes exhibited superparamagnetic properties at room temperature, associated with a magnetization of 12.6 emu/g. These Fe0.78Mn0.22O nanocubes present transversal (r2) and longitudinal (r1) relaxivities of 325.9 and 0.518 mM−1 s−1 at 7 T for water protons. The ratio of the r2/r1 (629.2) ranks them being the highest sensitivity (r2/r1) comparable to currently reported T2-weighted magnetic resonance imaging (MRI) agents. Meanwhile, the Fe0.78Mn0.22O nanocubes were functionalized and demonstrated to be biocompatible when attached to the surface of mesenchymal stem cells, therefore showing the promise as a new class of MRI agents in clinic applications.

Effects of Gold Nanospheres and Nanocubes on Amyloid-β Peptide Fibrillation.

Direct exposure or intake of engineered nanoparticles (ENPs) to the human body will trigger a series of complicated biological consequences. Especially, ENPs could either up- or downregulate peptide fibrillation, which is associated with various degenerative diseases like Alzheimer's and Parkinson's diseases. This work reports the effects of gold nanoparticles (AuNPs) with different shapes on the aggregation of an amyloid-β peptide (Aβ(1-40)) involved in Alzheimer's disease. Two kinds of AuNPs were investigated, i.e., gold nanospheres (AuNSs, ∼20 nm in diameter) and gold nanocubes (AuNCs, ∼20 nm in edge length). It was found that AuNPs play a catalytic role in peptide nucleation through interfacial adsorption of Aβ(1-40). AuNSs with hybrid facets have higher affinity to Aβ(1-40) because of the higher degree of surface atomic unsaturation than the {100}-faceted AuNCs. Therefore, AuNSs exert a more significant acceleration effect on the fibrillation process of Aβ(1-40) than AuNCs. Besides, a shape-dependent secondary structure transformation of Aβ(1-40) with different AuNPs was observed using Fourier transform infrared spectroscopy. The variation of peptide-NP and peptide-peptide interactions caused by the shape alteration of AuNPs influences the equilibrium of inter- and intramolecular hydrogen bonds, which is believed to be responsible for the shape-dependent secondary structure transformation. The study offers further understanding on the complicated NP-mediated Aβ aggregation and also facilitates further development on designing and synthesizing task-specific AuNPs for amyloid disease diagnosis and therapy.

Two-Dimensional, Hierarchical Ag-Doped TiO2 Nanocatalysts: Effect of the Metal Oxidation State on the Photocatalytic Properties

This paper reports the synthesis of two-dimensional, hierarchical, porous, and (001)-faceted metal (Ag, Zn, and Al)-doped TiO2 nanostructures (TNSs) and the study of their photocatalytic activity. Two-dimensional metal-doped TNSs were synthesized using the hydrolysis of ammonium hexafluorotitanate in the presence of hexamethylenetetramine and metal precursors. Typical morphology of metal-doped TNSs is a hierarchical nanosheet that is composed of randomly stacked nanocubes (dimensions of up to 5 μm and 200 nm in edge length and thickness, respectively) and has dominant (001) facets exposed. Raman analysis and X-ray photoelectron spectroscopy results indicated that the Ag doping, compared to Zn and Al, much improves the crystallinity degree and at the same time dramatically lowers the valence state binding energy of the TNS and provides an additional dopant oxidation state into the system for an enhanced electron-transfer process and surface reaction. These are assumed to enhance the photocatalytic of the TNS. In a model of photocatalytic reaction, that is, rhodamine B degradation, the AgTNS demonstrates a high photocatalytic activity by converting approximately 91% of rhodamine B within only 120 min, equivalent to a rate constant of 0.018 m–1 and ToN and ToF of 94 and 1.57 min–1, respectively, or 91.1 mmol mg–1 W–1 degradation when normalized to used light source intensity, which is approximately 2 times higher than the pristine TNS and several order higher when compared to Zn- and Al-doped TNSs. Improvement of the crystallinity degree, decrease in the defect density and the photogenerated electron and hole recombination, and increase of the oxygen vacancy in the AgTNS are found to be the key factors for the enhancement of the photocatalytic properties. This work provides a straightforward strategy for the preparation of high-energy (001) faceted, two-dimensional, hierarchical, and porous Ag-doped TNSs for potential use in photocatalysis and photoelectrochemical application.

Gold-Based Cubic Nanoboxes with Well-Defined Openings at the Corners and Ultrathin Walls Less Than Two Nanometers Thick.

We report a facile synthesis of Au-based cubic nanoboxes as small as 20 nm for the outer edge length, together with well-defined openings at the corners and walls fewer than 10 atomic layers (or <2 nm) in thickness. The success relies on the selective formation of Ag2O at the corners of Ag nanocubes, followed by the conformal deposition of Au on the side faces in a layer-by-layer fashion. When six atomic layers of Au are formed on the side faces to generate Ag@Au6L core-shell nanocubes, we can selectively remove the Ag2O patches at the corner sites using a weak acid, making it possible to further remove the Ag core by H2O2 etching without breaking the ultrathin Au shell. This synthetic approach works well for Ag nanocubes of 38 and 18 nm in edge length, and the wall thickness of the nanoboxes can be controlled down to 2 nm. The resultant Au nanoboxes exhibit strong plasmonic absorption in the near-infrared region, consistent with computational simulations.

Coating Pt-Ni Octahedra with Ultrathin Pt Shells to Enhance the Durability without Compromising the Activity toward Oxygen Reduction.

We describe a new strategy to enhance the catalytic durability of Pt-Ni octahedral nanocrystals in the oxygen reduction reaction (ORR) by conformally depositing an ultrathin Pt shell on the surface. The Pt-Ni octahedra were synthesized according to a protocol reported previously and then employed directly as seeds for the conformal deposition of ultrathin Pt shells by introducing a Pt precursor dropwise at 200 °C. The amount of Pt precursor was adjusted relative to the number of Pt-Ni octahedra involved to obtain Pt-Ni@Pt1.5L octahedra of 12 nm in edge length for the systematic evaluation of their chemical stability and catalytic durability compared to Pt-Ni octahedra. Specifically, we compared the elemental compositions of the octahedra before and after treatment with acetic and sulfuric acids. We also examined their electrocatalytic stability toward the ORR through an accelerated durability test by using a rotating disk electrode method. Even after treatment with sulfuric acid for 24 h, the Pt-Ni@Pt1.5L octahedra maintained their original Ni content, whereas 11 % of the Ni was lost from the Pt-Ni octahedra. After 10 000 cycles of ORR, the mass activity of the Pt-Ni octahedra decreased by 75 %, whereas the Pt-Ni@Pt1.5L octahedra only showed a 25 % reduction.

Synthesis of Pt-Ni Octahedra in Continuous-Flow Droplet Reactors for the Scalable Production of Highly Active Catalysts toward Oxygen Reduction.

A number of groups have reported the syntheses of nanosized Pt-Ni octahedra with remarkable activities toward the oxygen reduction reaction (ORR), a process key to the operation of proton-exchange membrane fuel cells. However, the throughputs of those batch-based syntheses are typically limited to a scale of 5-25 mg Pt per batch, which is far below the amount needed for commercial evaluation. Here we report the use of droplet reactors for the continuous and scalable production of Pt-Ni octahedra with high activities toward ORR. In a typical synthesis, Pt(acac)2, Ni(acac)2, and W(CO)6 were dissolved in a mixture of oleylamine, oleic acid, and benzyl ether, and then pumped into a polytetrafluoroethylene tube. When the solution entered the reaction zone at a temperature held in the range of 170-230 °C, W(CO)6 quickly decomposed to generate CO gas, naturally separating the reaction solution into discrete, uniform droplets. Each droplet then served as a reactor for the nucleation and growth of Pt-Ni octahedra whose size and composition could be controlled by changing the composition of the solvent and/or adjusting the amount of Ni(acac)2 added into the reaction solution. For a catalyst based on Pt2.4Ni octahedra of 9 nm in edge length, it showed an ORR mass activity of 2.67 A mgPt(-1) at 0.9 V, representing an 11-fold improvement over a state-of-the-art commercial Pt/C catalyst (0.24 A mgPt(-1)).

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.

Shape effect on the antibacterial activity of silver nanoparticles synthesized via a microwave-assisted method.

Silver nanoparticles (AgNPs) are used as sustained-release bactericidal agents for water treatment. Among the physicochemical characteristics of AgNPs, shape is an important parameter relevant to the antibacterial activity. Three typically shaped AgNPs, nanocubes, nanospheres, and nanowires, were prepared via a microwave-assisted method and characterized by TEM, UV-vis, and XRD. The antibacterial activity of AgNPs was determined by OD growth curves tests, MIC tests, and cell viability assay against Escherichia coli. The interaction between AgNPs and bacterial cells was observed by TEM. The results showed that the three differently shaped AgNPs were nanoscale, 55 ± 10 nm in edge length for nanocubes, 60 ± 15 nm in diameter for nanospheres, 60 ± 10 nm in diameter and 2-4 μm in length for nanowires. At the bacterial concentration of 10(4) CFU/mL, the MIC of nanocubes, nanospheres, and nanowires were 37.5, 75, and 100 μg/mL, respectively. Due to the worst contact with bacteria, silver nanowires exhibited the weakest antibacterial activity compared with silver nanocubes and silver nanospheres. Besides, silver nanocubes mainly covered by {100} facets showed stronger antibacterial activity than silver nanospheres covered by {111} facets. It suggests that the shape effect on the antibacterial activity of AgNPs is attributed to the specific surface areas and facets reactivity; AgNPs with larger effective contact areas and higher reactive facets exhibit stronger antibacterial activity.

Size dependence of simulated optical properties for Cu nanocubes

This paper reports a systematic investigation on the optical properties of Cu nanocubes as a function of the edge length by the discrete dipole approximation. In the far-field, our results showed that the extinction resonance peak shifted to long wavelength from 595 nm to 670 nm as the size increased from 10 nm to 90 nm. Also, the highest optical efficiencies for absorption and scattering were obtained for the nanocubes that were 50 nm and 90 nm in size, respectively. In the near field, the effects of the edge length on the local electric field were investigated considering the extinction spectra peak as the excitation wavelength. The near field intensity increased with size from 10 nm to 60 nm, being the highest at the excitation wavelength of 630 nm in edge length of 60 nm, followed by a decrease at larger sizes. The size dependence of far-field and near-field optical properties described here can guide design of plasmonic nanostructures for applications in nonlinear spectroscopy, near-field lithography and plasmonic solar cells.

Continuous and scalable production of well-controlled noble-metal nanocrystals in milliliter-sized droplet reactors.

Noble-metal nanocrystals are essential to applications in a variety of areas, including catalysis, electronics, and photonics. Despite the large number of reports, there still exists a gap between academic studies and industrial applications due to the lack of ability to produce the nanocrystals in large quantities while still maintaining the good uniformity and precise controls. Because the nucleation and growth of colloidal nanocrystals are highly sensitive to experimental conditions, it is impractical to scale up their production by simply increasing the reaction volume. Here we report a new and practical approach based on milliliter-sized droplet reactors to the scalable production of nanocrystals. The droplets of 0.25 mL in volume were produced as a continuous flow in a fluidic device assembled from commercially available components. As a proof of concept, we have synthesized Pd, Au, and Pd-M (M = Au, Pt, and Ag) nanocrystals with controlled sizes, shapes, compositions, and structures on a scale of 1-10 g per hour (e.g., 3.6 g per hour for Pd cubes of 10 nm in edge length).

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.

Face-Raised Octahedral Co3O4 Nanocrystals and Their Catalytic Activity in the Selective Oxidation of Alcohols

Face-raised Co3O4 octahedral crystals were successfully constructed through a carbon-assisted method using cellulose as carbon resource and used for a catalyst for selective oxidation of alcohols. The face-raised Co3O4 octahedra are about 200 nm in edge length and assembled to microtubes with a length of ca. 10 μm and a width of 2–3 μm. Our analysis showed that the thermal decomposition and carbonization of cellulose has contributed to the generation of the octahedral structure and the assembled process. Moreover, compared with normal Co3O4 octahedra, the face-raised Co3O4 octahedral crystals have higher remanence and saturation magnetization, which is attributed to their more uniform small grain sizes. In particular, the face-raised Co3O4 octahedra gave both higher activity and higher selectivity than the normal Co3O4 octahedra in the catalytic oxidation reactions of alcohols. More importantly, after eight cycles, the face-raised Co3O4 octahedral crystals still exhibited considerably high catalytic activity, suggesting promising applications in heterocatalysis.

Fabrication of silver nanosheets on quartz glass substrates through electroless plating approach

Silver nanosheets (NSs) have been synthesized by an electroless plating approach using a complexation mechanism of triethanolamine (TEA) and Ag+ to reduce the oxidation–reduction potential difference and slow down the deposition speed of Ag on quartz glass substrates. The synthesized Ag NSs with 500 nm in edge length and 30 nm in thickness stand on the substrates and are dispersed uniformly. The formation mechanism of Ag NSs is proposed. The formation of Ag NSs is attributed to the molar ratio of AgNO3 to TEA, the concentration of AgNO3 and the influence of reaction temperature. This study is important in vertical immobilization Ag NSs on solid substrates, which could provide substrates for catalysis or surface-enhanced Raman scattering.

Synthesis of Ag Nanocubes 18–32 nm in Edge Length: The Effects of Polyol on Reduction Kinetics, Size Control, and Reproducibility

This article describes a robust method for the facile synthesis of small Ag nanocubes with edge lengths controlled in the range of 18-32 nm. The success of this new method relies on the substitution of ethylene glycol (EG)--the solvent most commonly used in a polyol synthesis--with diethylene glycol (DEG). Owing to the increase in hydrocarbon chain length, DEG possesses a higher viscosity and a lower reducing power relative to EG. As a result, we were able to achieve a nucleation burst in the early stage to generate a large number of seeds and a relatively slow growth rate thereafter; both factors were critical to the formation of Ag nanocubes with small sizes and in high purity (>95%). The edge length of the Ag nanocubes could be easily tailored in the range of 18-32 nm by quenching the reaction at different time points. For the first time, we were able to produce uniform sub-20 nm Ag nanocubes in a hydrophilic medium and on a scale of ∼20 mg per batch. It is also worth pointing out that the present protocol was remarkably robust, showing good reproducibility between different batches and even for DEGs obtained from different vendors. Our results suggest that the high sensitivity of synthesis outcomes to the trace amounts of impurities in a polyol, a major issue for reproducibility and scale up synthesis, did not exist in the present system.

Au@Pd core–shell nanocubes with finely-controlled sizes

We report a facile method for the synthesis of highly uniform Au@Pd core–shell nanocubes with finely- and well-controlled sizes by seed-mediated growth. Using single-crystal seeds of Au spheres with a uniform size, we could reproducibly obtain Au@Pd core–shell nanocubes with a narrow size distribution ( 98%). Moreover, the size of the Au@Pd core–shell nanocubes could be finely and readily tuned in a controllable fashion from 11.4 to 41.1 nm in edge length by varying the concentration of Na2PdCl4, the amount of seeds, or both. We have also investigated the localized surface plasmon resonance properties of Au@Pd core–shell nanocubes as a function of Pd shell thickness.