Colorimetric Detection of Fentanyl Powder on Surfaces Using a Supramolecular Displacement Assay.

Fentanyl is a potent synthetic opioid with an alarmingly low lethal dosage of 2 mg. The equipment necessary to detect fentanyl in field settings (e.g., hand-held spectrometers) is restricted to highly trained, well-funded, and specialized personnel. Established point-of-need technologies, such as lateral flow immunochromatographic strips, are available; however, they often involve multiple contact-based steps (e.g., collection, mixing) that pose a higher risk to users handling unknown substances. Herein, we developed a colorimetric displacement assay capable of contactless detection of fentanyl in liquid or solid samples. The basis of our assay relies on the presence of fentanyl to displace a redox mediator, ferrocene carboxylic acid, inclusively bound in the cavity of a supramolecular host, CB[7]. The displacement is only possible in the presence of high affinity binding guests, like fentanyl (KA ∼ 106 M-1). The liberated redox guest can then react with indicator reagents that are free in solution, producing either: (i) a distinct blue color to indicate the presence of fentanyl or (ii) a pale blue tint in the absence of fentanyl. We demonstrate rapid and specific detection of fentanyl free base and fentanyl derivatives (e.g., acetyl fentanyl and furanyl fentanyl) against a panel of 9 other common drugs of abuse (e.g., morphine, cocaine, and heroin). Furthermore, we highlight the intended use of this assay by testing grains of fentanyl derivatives on a surface with a drop (i.e., 25 µL) of the assay reagent. We anticipate that this approach can be applied broadly to identify the presence of fentanyl at the point of need.

Ruthenium Nanoframes in the Face-Centered Cubic Phase: Facile Synthesis and Their Enhanced Catalytic Performance.

Owing to their highly open structure and a large number of low-coordination sites on the surface, noble-metal nanoframes are intriguing for catalytic applications. Here, we demonstrate the rational synthesis of Ru cuboctahedral nanoframes with enhanced catalytic performance toward hydrazine decomposition. The synthesis starts from Pd nanocubes, which quickly undergo truncation at the corners as a consequence of oxidative etching caused by Br- ions. Afterward, the galvanic replacement reaction between Pd and Ru(III) ions dominates, leading to the selective deposition of Ru atoms on the corners and edges and thereby the fabrication of Pd@Ru core-frame cuboctahedra. Significantly, the deposited Ru atoms are crystallized in a face-centered cubic (fcc) phase instead of the hexagonal close-packed (hcp) structure typical of bulk Ru. Upon the removal of Pd remaining in the core via chemical etching, we obtain Ru cuboctahedral nanoframes. By varying the amount of the Ru(III) precursor, the ridge thickness of the nanoframes can be tuned from a few atomic layers up to 10. Both the frame structure and fcc crystal phase of the Ru cuboctahedral nanoframes can be well preserved up to 300 °C. When compared with hcp-Ru nanoparticles, the fcc-Ru nanoframes displayed substantial enhancement in terms of H2 selectivity toward hydrazine decomposition. This work offers the opportunity to engineer both the morphology and crystal phase of Ru nanocrystals for catalytic applications.

Ru Octahedral Nanocrystals with a Face-Centered Cubic Structure, {111} Facets, Thermal Stability up to 400 °C, and Enhanced Catalytic Activity.

Ruthenium nanocrystals with both a face-centered cubic ( fcc) structure and well-controlled facets are attractive catalytic materials for various reactions. Here we report a simple method for the synthesis of Ru octahedral nanocrystals with an fcc structure and an edge length of 9 nm. The success of this synthesis relies on the use of 4.5 nm Rh cubes as seeds to facilitate the heterogeneous nucleation and overgrowth of Ru atoms. We choose Rh because it can resist oxidative etching under the harsh conditions for Ru overgrowth, it can be readily prepared as nanocubes with edge lengths less than 5 nm, and its atoms have a size close to that of Ru atoms. During the seed-mediated growth, the atomic packing of Ru overlayers follows an fcc lattice, in contrast to the conventional hexagonal close-packed ( hcp) lattice associated with bulk Ru. The final product takes an octahedral shape, with the surface enclosed by {111} facets. Our in situ measurements suggest that both the octahedral shape and the fcc crystal structure can be well preserved up to 400 °C, which is more than 100 °C higher than what was reported for Ru octahedral nanocages. When utilized as catalysts, the Ru octahedral nanocrystals exhibited 4.4-fold enhancement in terms of specific activity toward oxygen evolution relative to hcp-Ru nanoparticles. We also demonstrate that Ru{111} facets are more active than Ru{100} facets in catalyzing the oxygen evolution reaction. Altogether, this work offers an effective method for the synthesis of Ru nanocrystals with an fcc structure and well-defined {111} facets, as well as enhanced thermal stability and catalytic activity. We believe these nanocrystals will find use in various catalytic applications.

One-Pot Synthesis of Pd@PtnL Core-Shell Icosahedral Nanocrystals in High Throughput through a Quantitative Analysis of the Reduction Kinetics.

The rational design and implementation of a one-pot method is reported for the facile synthesis of Pd@PtnL (nL denotes the number of Pt atomic layers) core-shell icosahedral nanocrystals in a single step. The success of this method relies on the use of Na2 PdCl4 and Pt(acac)2 as the precursors to Pd and Pt atoms, respectively. Our quantitative analysis of the reduction kinetics indicates that the PdII and PtII precursors are sequentially reduced with a major gap between the two events. Specifically, the PdII precursor is reduced first, leading to the formation of Pd-based icosahedral seeds with a multiply-twinned structure. In contrast, the PtII precursor prefers to take a surface reduction pathway on the just-formed icosahedral seeds. As such, the otherwise extremely slow reduction of the PtII precursor can be dramatically accelerated through an autocatalytic process for the deposition of Pt atoms as a conformal shell on each Pd icosahedral core. Compared to the conventional approach of seed-mediated growth, the throughput for the one-pot synthesis of Pd@PtnL core-shell nanocrystals can be increased by more than 30-fold. When used as catalysts, the Pd@Pt4.5L core-shell icosahedral nanocrystals show specific and mass activities of 0.83 mA cm-2 and 0.39 A mgPt -1 , respectively, at 0.9 V toward oxygen reduction. The Pt-based nanocages derived from the core-shell nanocrystals also show enhanced specific (1.45 mA cm-2 ) and mass activities (0.75 A mgPt -1 ) at 0.9 V, which are 3.8 and 3.3 times greater than those of the commercial Pt/C, respectively.

Synthesis of Palladium Nanoscale Octahedra through a One-Pot, Dual-Reductant Route and Kinetic Analysis.

Shape-controlled synthesis of colloidal metal nanocrystals has traditionally relied on the use of an approach that involves the reduction of a metal precursor by a single reductant. Once the concentration of atoms surpasses supersaturation, they will undergo homogeneous nucleation to generate nuclei and then seeds, followed by further growth into nanocrystals. In general, it is a grand challenge to optimize such an approach because the kinetic requirement for nucleation tends to be drastically different from what is needed to guide the growth process. In this work, we overcome this difficulty by switching to a dual-reductant approach, in which both strong and weak reductants are added into the same reaction solution. By controlling their amounts to program the reduction kinetics, the strong reductant only regulates the homogeneous nucleation process to generate the desired seeds, and once consumed, the weak reductant takes over to control the growth pattern and thereby the shape of the resulting nanocrystals.

On the Thermodynamics and Experimental Control of Twinning in Metal Nanocrystals.

This work demonstrates a new strategy for controlling the evolution of twin defects in metal nanocrystals by simply following thermodynamic principles. With Ag nanocrystals supported on amorphous SiO2 as a typical example, we establish that twin defects can be rationally generated by equilibrating nanoparticles of different sizes through heating and then cooling. We validate that Ag nanocrystals with icosahedral, decahedral, and single-crystal structures are favored at sizes below 7 nm, between 7 and 11 nm, and greater than 11 nm, respectively. This trend is then rationalized by computational studies based on density functional theory and molecular dynamics, which show that the excess free energy for the three equilibrium structures correlate strongly with particle size. This work not only highlights the importance of thermodynamic control but also adds another synthetic method to the ever-expanding toolbox used for generating metal nanocrystals with desired properties.

Understanding the Thermal Stability of Palladium-Platinum Core-Shell Nanocrystals by In Situ Transmission Electron Microscopy and Density Functional Theory.

Core-shell nanocrystals offer many advantages for heterogeneous catalysis, including precise control over both the surface structure and composition, as well as reduction in loading for rare and costly metals. Although many catalytic processes are operated at elevated temperatures, the adverse impacts of heating on the shape and structure of core-shell nanocrystals are yet to be understood. In this work, we used ex situ heating experiments to demonstrate that Pd@Pt4L core-shell nanoscale cubes and octahedra are promising for catalytic applications at temperatures up to 400 °C. We also used in situ transmission electron microscopy to monitor the thermal stability of the core-shell nanocrystals in real time. Our results demonstrate a facet dependence for the thermal stability in terms of shape and composition. Specifically, the cubes enclosed by {100} facets readily deform shape at a temperature 300 °C lower than that of the octahedral counterparts enclosed by {111} facets. A reversed trend is observed for composition, as alloying between the Pd core and the Pt shell of an octahedron occurs at a temperature 200 °C lower than that for the cubic counterpart. Density functional theory calculations provide atomic-level explanations for the experimentally observed behaviors, demonstrating that the barriers for edge reconstruction determine the relative ease of shape deformation for cubes compared to octahedra. The opposite trend for alloying of the core-shell structure can be attributed to a higher propensity for subsurface Pt vacancy formation in octahedra than in cubes.

Synthesis and Characterization of Pt-Ag Alloy Nanocages with Enhanced Activity and Durability toward Oxygen Reduction.

Engineering the elemental composition of metal nanocrystals offers an effective strategy for the development of catalysts or electrocatalysts with greatly enhanced activity. Herein, we report the synthesis of Pt-Ag alloy nanocages with an outer edge length of 18 nm and a wall thickness of about 3 nm. Such nanocages with a composition of Pt19Ag81 could be readily prepared in one step through the galvanic replacement reaction between Ag nanocubes and a Pt(II) precursor. After 10 000 cycles of potential cycling in the range of 0.60-1.0 V as in an accelerated durability test, the composition of the nanocages changed to Pt56Ag44, together with a specific activity of 1.23 mA cm-2 toward oxygen reduction, which was 3.3 times that of a state-of-the-art commercial Pt/C catalyst (0.37 mA cm-2) prior to durability testing. Density functional theory calculations attributed the increased activity to the stabilization of the transition state for breaking the O-O bond in molecular oxygen. Even after 30 000 cycles of potential cycling, the mass activity of the nanocages only dropped from 0.64 to 0.33 A mg-1Pt, which was still about two times that of the pristine Pt/C catalyst (0.19 A mg-1Pt).

Platinum Cubic Nanoframes with Enhanced Catalytic Activity and Durability Toward Oxygen Reduction.

We report the synthesis and electrocatalytic properties of Pt cubic nanoframes with ultrathin ridges less than 2 nm in thickness. The nanoframes were synthesized through site-selected deposition of Pt onto the corner and edge sites of Pd nanocubes, followed by selective removal of the Pd cores via chemical etching. The Br- ions chemisorbed on the side faces of a Pd nanocube played a critical role in enabling the siteselected deposition. In addition, the kinetics of deposition and the diffusion of Pt adatoms was optimized by carefully controlling the injection rate of the Pt precursor and the reaction temperature, respectively, to obtain the frame-like structure. When benchmarked against a commercial Pt/C comprised of Pt particles 2-3 nm in size, the Pt frame/C catalyst exhibited not only enhanced mass activity toward oxygen reduction, but also substantially improved catalytic durability. In an accelerated durability test, the Pt frame/C catalyst showed a mass activity more than 6× greater than for the Pt/C reference after 20 000 cycles of repeated potential sweeping. This improvement can be largely attributed to the frame-like structure, which is unique in suppressing both the detachment and aggregation of catalytic particles owing to the significantly enhanced interaction with carbon support.

Quantitative Analysis of the Reduction Kinetics Responsible for the One-Pot Synthesis of Pd-Pt Bimetallic Nanocrystals with Different Structures.

We report a quantitative understanding of the reduction kinetics responsible for the formation of Pd-Pt bimetallic nanocrystals with two distinctive structures. The syntheses involve the use of KBr to manipulate the reaction kinetics by influencing the redox potentials of metal precursor ions via ligand exchange. In the absence of KBr, the ratio between the initial reduction rates of PdCl4(2-) and PtCl4(2-) was about 10.0, leading to the formation of Pd@Pt octahedra with a core-shell structure. In the presence of 63 mM KBr, the products became Pd-Pt alloy nanocrystals. In this case, the ratio between the initial reduction rates of the two precursors dropped to 2.4 because of ligand exchange and, thus, the formation of PdBr4(2-) and PtBr4(2-). The alloy nanocrystals took a cubic shape owing to the selective capping effect of Br(-) ions toward the {100} facets. Relative to the alloy nanocubes, the Pd@Pt core-shell octahedra showed substantial enhancement in both catalytic activity and durability toward the oxygen reduction reaction (ORR). Specifically, the specific (1.51 mA cm(-2)) and mass (1.05 A mg(-1) Pt) activities of the core-shell octahedra were enhanced by about four- and three-fold relative to the alloy nanocubes (0.39 mA cm(-2) and 0.34 A mg(-1) Pt, respectively). Even after 20000 cycles of accelerated durability test, the core-shell octahedra still exhibited a mass activity of 0.68 A mg(-1) Pt, twice that of a pristine commercial Pt/C catalyst.

Synthesis and Characterization of Ru Cubic Nanocages with a Face-Centered Cubic Structure by Templating with Pd Nanocubes.

Nanocages have received considerable attention in recent years for catalytic applications owing to their high utilization efficiency of atoms and well-defined facets. Here we report, for the first time, the synthesis of Ru cubic nanocages with ultrathin walls, in which the atoms are crystallized in a face-centered cubic (fcc) rather than hexagonal close-packed (hcp) structure. The key to the success of this synthesis is to ensure layer-by-layer deposition of Ru atoms on the surface of Pd cubic seeds by controlling the reaction temperature and the injection rate of a Ru(III) precursor. By selectively etching away the Pd from the Pd@Ru core-shell nanocubes, we obtain Ru nanocages with an average wall thickness of 1.1 nm or about six atomic layers. Most importantly, the Ru nanocages adopt an fcc crystal structure rather than the hcp structure observed in bulk Ru. The synthesis has been successfully applied to Pd cubic seeds with different edge lengths in the range of 6-18 nm, with smaller seeds being more favorable for the formation of Ru shells with a flat, smooth surface due to shorter distance for the surface diffusion of the Ru adatoms. Self-consistent density functional theory calculations indicate that these unique fcc-structured Ru nanocages might possess promising catalytic properties for ammonia synthesis compared to hcp Ru(0001), on the basis of strengthened binding of atomic N and substantially reduced activation energies for N2 dissociation, which is the rate-determining step for ammonia synthesis on hcp Ru catalysts.

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.

NANOCATALYSTS. Platinum-based nanocages with subnanometer-thick walls and well-defined, controllable facets.

A cost-effective catalyst should have a high dispersion of the active atoms, together with a controllable surface structure for the optimization of activity, selectivity, or both. We fabricated nanocages by depositing a few atomic layers of platinum (Pt) as conformal shells on palladium (Pd) nanocrystals with well-defined facets and then etching away the Pd templates. Density functional theory calculations suggest that the etching is initiated via a mechanism that involves the formation of vacancies through the removal of Pd atoms incorporated into the outermost layer during the deposition of Pt. With the use of Pd nanoscale cubes and octahedra as templates, we obtained Pt cubic and octahedral nanocages enclosed by {100} and {111} facets, respectively, which exhibited distinctive catalytic activities toward oxygen reduction.

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.