FePt Nanoparticles Assembled on Graphene as Enhanced Catalyst for Oxygen Reduction Reaction

Seven-nanometer FePt nanoparticles (NPs) were synthesized and assembled on graphene (G) by a solution-phase self-assembly method. These G/FePt NPs were a more active and durable catalyst for oxygen reduction reaction (ORR) in 0.1 M HClO₄ than the same NPs or commercial Pt NPs deposited on conventional carbon support. The G/FePt NPs annealed at 100 °C for 1 h under Ar + 5% H₂ exhibited specific ORR activities of 1.6 mA/cm² at 0.512 V and 0.616 mA/cm² at 0.557 V (vs Ag/AgCl). As a comparison, the commercial Pt NPs (2–3 nm) had specific activities of 0.271 and 0.07 mA/cm² at the same potentials. The G/FePt NPs were also much more stable in the ORR condition and showed nearly no activity change after 10 000 potential sweeps. The work demonstrates that G is indeed a promising support to improve NP activity and durability for practical catalytic applications

Pd Nanowires as New Biosensing Materials for Magnified Fluorescent Detection of Nucleic Acid

The designed synthesis of new nanomaterials with controlled shape, composition, and structure is critical for tuning their physical and chemical properties, and further developing interesting analytical sensing devices. Herein, we presented that Pd nanowires (NWs) can be used as a new biosensing platform for high-sensitivity nucleic acid detection. The general sensing concept is based on the fact that Pd NWs can adsorb the fluorescently labeled single-stranded DNA probe and lead to substantial fluorescence quenching of dye, followed by specific hybridization with the complementary region of the target DNA sequence. This results in desorption of double-stranded DNA from Pd NWs surface and subsequent recovery of fluorescence. Furthermore, an amplification strategy based on Pd NWs for nucleic acid detection by using exonuclease III (Exo III) was demonstrated. The present dual-magnification sensing system combined Pd NWs with Exo III has a detection range of 1.0 nM to 2.0 μM with the detection limit of 0.3 nM (S/N = 3), which is about 20-fold higher than that of traditional unamplified homogeneous assays

A Dynamic Structure for High-Dimensional Covariance Matrices and Its Application in Portfolio Allocation

<p>Estimation of high-dimensional covariance matrices is an interesting and important research topic. In this article, we propose a dynamic structure and develop an estimation procedure for high-dimensional covariance matrices. Asymptotic properties are derived to justify the estimation procedure and simulation studies are conducted to demonstrate its performance when the sample size is finite. By exploring a financial application, an empirical study shows that portfolio allocation based on dynamic high-dimensional covariance matrices can significantly outperform the market from 1995 to 2014. Our proposed method also outperforms portfolio allocation based on the sample covariance matrix, the covariance matrix based on factor models, and the shrinkage estimator of covariance matrix. Supplementary materials for this article are available online.</p

Ultrathin Laminar Ir Superstructure as Highly Efficient Oxygen Evolution Electrocatalyst in Broad pH Range

Shape-controlled noble metal nanocrystals (NCs), such as Au, Ag, Pt, Pd, Ru, and Rh are of great success due to their new and enhanced properties and applications in chemical conversion, fuel cells, and sensors, but the realization of shape control of Ir NCs for achieving enhanced electrocatalysis remains a significant challenge. Herein, we report an efficient solution method for a new class of three-dimensional (3D) Ir superstructure that consists of ultrathin Ir nanosheets as subunits. Electrochemical studies show that it delivers the excellent electrocatalytic activity toward oxygen evolution reaction (OER) in alkaline condition with an onset potential at 1.43 V versus reversible hydrogen electrode (RHE) and a very low Tafel slope of 32.7 mV decade^–1. In particular, it even shows superior performance for OER in acidic solutions with the low onset overpotential of 1.45 V versus RHE and small Tafel slope of 40.8 mV decade^–1, which are much better than those of small Ir nanoparticles (NPs). The 3D Ir superstructures also exhibit good stability under acidic condition with the potential shift of less than 20 mV after 8 h i-t test. The present work highlights the importance of tuning 3D structures of Ir NCs for enhancing OER performance

Screw Thread-Like Platinum–Copper Nanowires Bounded with High-Index Facets for Efficient Electrocatalysis

Introducing high-index facets into nanocrystals (NCs) is an effective way for boosting the electrocatalytic intrinsic activity. However, the established NCs with high-index facets usually have a big diameter, which makes them exhibit a very limited surface area, thus finally limited mass activity. To embody the advantage of high-index facets in enhancing electrocatalysis well, the better nanostructures should meet the requirement of both high surface area and high-density high-index facets. Herein, we report our important advances in making the unique three-dimensional screw thread-like platinum–copper (Pt–Cu) alloy nanowires (NWs) with high-density high-index facets and controlled composition. Such special NWs with a high surface area of 46.90 m² g^–1 exhibit much better performance than the PtCu nanoparticles (NPs) in alcohol electrooxidations. This work opens a new way for maximizing the electrocatalytic performance by introducing high-index facets into high-surface-area stable bimetallic NWs

Tuning the Aggregation/Disaggregation Behavior of Graphene Quantum Dots by Structure-Switching Aptamer for High-Sensitivity Fluorescent Ochratoxin A Sensor

The design of graphene quantum dots (GQDs)-aptamer bioconjugates as the new sensing platform is very important for developing high-sensitivity fluorescent biosensors; however, achieving new bioconjugates is still a great challenge. Herein, we report the development of a new high-sensitivity fluorescent aptasensor for the detection of ochratoxin A (OTA) based on tuning aggregation/disaggregation behavior of GQDs by structure-switching aptamers. The fluorescence sensing process for OTA detection involved two key steps: (1) cDNA-aptamer (cDNA, complementary to part of the OTA aptamer) hybridization induced the aggregation of GQD (fluorescence quenching) after cDNA was added into the GQDs-aptamer bioconjugate solution, and (2) the target of OTA triggered disaggregation of GQD aggregates (fluorescence recovery). Such new fluorescent sensing platform can be used to monitor OTA with a linear range of 0 to 1 ng/mL and very low detection limit of 13 pg/mL, which is among the best in all the developed fluorescent nanoparticles-based sensors. Such sensing strategy is also successful in analyzing OTA in practical red wine sample with 94.4–102.7% of recoveries and relative standard deviation in the range of 2.9–5.8%. The present works open a new way for signaling the target-aptamer binding event by tuning aggregation/disaggregation behavior of GQDs-bioconjugates

Room Temperature Single-Photon Emission from Individual Perovskite Quantum Dots

Lead-halide-based perovskites have been the subject of numerous recent studies largely motivated by their exceptional performance in solar cells. Electronic and optical properties of these materials have been commonly controlled by varying the composition (<i>e.g.</i>, the halide component) and/or crystal structure. Use of nanostructured forms of perovskites can provide additional means for tailoring their functionalities <i>via</i> effects of quantum confinement and wave function engineering. Furthermore, it may enable applications that explicitly rely on the quantum nature of electronic excitations. Here, we demonstrate that CsPbX₃ quantum dots (X = I, Br) can serve as room-temperature sources of quantum light, as indicated by strong photon antibunching detected in single-dot photoluminescence measurements. We explain this observation by the presence of fast nonradiative Auger recombination, which renders multiexciton states virtually nonemissive and limits the fraction of photon coincidence events to ∼6% on average. We analyze limitations of these quantum dots associated with irreversible photodegradation and fluctuations (“blinking”) of the photoluminescence intensity. On the basis of emission intensity-lifetime correlations, we assign the “blinking” behavior to random charging/discharging of the quantum dot driven by photoassisted ionization. This study suggests that perovskite quantum dots hold significant promise for applications such as quantum emitters; however, to realize this goal, one must resolve the problems of photochemical stability and photocharging. These problems are largely similar to those of more traditional quantum dots and, hopefully, can be successfully resolved using advanced methodologies developed over the years in the field of colloidal nanostructures

Trimetallic PtSnRh Wavy Nanowires as Efficient Nanoelectrocatalysts for Alcohol Electrooxidation

The design and creation of efficient catalysts for alcohol oxidation reaction has attracted great research attention because alcohols are promising fuels for direct fuel cell reactions because of their high energy density, easy storage, and transportation. We herein report an efficient strategy that allows the preparation of ternary PtSnM (M = Co, Ni, and Rh) wavy nanowires (WNWs) with ultrathin diameter of only around 2 nm and tunable compositions in high yield. Detailed catalytic studies show that all the ternary WNWs exhibit high performance for ethanol oxidation reaction (EOR) and methanol oxidation reaction (MOR), and their performance shows interesting composition-dependent electrocatalytic activity with PtSnRh WNWs having the best activity for both EOR and MOR. The PtSnRh WNWs are also more stable than commercial Pt/C catalyst, as revealed by long-time chronoamperometric (CA) measurements. The present work highlights the use of multimetallic WNWs as highly active and durable nanocatalysts in enhancing alcohol electrooxidation, which will open a new way in tuning 1D multimetallic nanostructures for boosting other fuel cell reactions, various heterogeneous reactions, and beyond

Synthetic Control of FePtM Nanorods (M = Cu, Ni) To Enhance the Oxygen Reduction Reaction

To further enhance the catalytic activity and durability of nanocatalysts for the oxygen reduction reaction (ORR), we synthesized a new class of 20 nm × 2 nm ternary alloy FePtM (M = Cu, Ni) nanorods (NRs) with controlled compositions. Supported on carbon support and treated with acetic acid as well as electrochemical etching, these FePtM NRs were converted into core/shell FePtM/Pt NRs. These core/shell NRs, especially FePtCu/Pt NRs, exhibited much improved ORR activity and durability. The Fe₁₀Pt₇₅Cu₁₅ NRs showed a mass current densities of 1.034 A/mg_Pt at 512 mV vs Ag/AgCl and 0.222 A/mg_Pt at 557 mV vs Ag/AgCl, which are much higher than those for a commercial Pt catalyst (0.138 and 0.035 A/mg_Pt, respectively). Our controlled synthesis provides a general approach to core/shell NRs with enhanced catalysis for the ORR or other chemical reactions

Crystalline Control of {111} Bounded Pt₃Cu Nanocrystals: Multiply-Twinned Pt₃Cu Icosahedra with Enhanced Electrocatalytic Properties

Despite that different facets have distinct catalytic behavior, the important role of twin defects on enhancing the catalytic performance of metallic nanocrystals is largely unrevealed. The key challenge in demonstrating the importance of twin defects for catalysis is the extreme difficulties in creating nanostructures with the same exposed facets but tunable twin defects that are suitable for catalytic investigations. Herein, we show an efficient synthetic strategy to selectively synthesize {111}-terminated Pt₃Cu nanocrystals with controllable crystalline features. Two distinct {111}-bounded shapes, namely, multiply-twinned Pt₃Cu icosahedra and single-crystalline Pt₃Cu octahedra, are successfully prepared by simply changing the types of Cu precursors with the other growth parameters unchanged. Electrocatalytic studies show that the {111}-terminated Pt₃Cu nanocrystals exhibit the very interesting crystalline nature-dependent electrocatalytic activities toward both the oxygen reduction reaction (ORR) and methanol oxidation reaction (MOR) with multiply-twinned Pt₃Cu icosahedra demonstrating enhanced electrocatalytic activities compared to the single-crystalline Pt₃Cu octahedra due to their additional yet important effect of twin defect. As a result, under the multiple tuning conditions (alloy, shape, and twin effects), the multiply-twinned Pt₃Cu icosahedra exhibit much enhanced electrocatalytic activities in both ORR and MOR with respect to the Pt black. The present work highlights the importance of twin defects in enhancing electrocatalytic activities of metallic nanocrystals