Intensity-Dependent Enhancement of Saturable Absorption in PbS-Au4 Nanohybrid Composites: Evidence for Resonant Energy Transfer by Auger Recombination

Intensity-dependent enhancement of saturable absorption in a film of PbS-Au4 nanohybrid composites has been observed by femtosecond time-resolved transient absorption measurement at 780 nm. The nonlinear absorption coefficient of saturable absorption in PbS-Au4 nanohybrid composites is found to be dependent on excitation irradiance and it is determined to be -2.9 cm/GW at 78 GW/cm2, an enhancement of nearly fourfold in comparison with that of pure PbS quantum dots (QDs). The enhancement is attributed to excitation of surface plasmon by resonant energy transfer between PbS QDs and Au nanoparticles through Auger recombination.Comment: 14 pages, 3 figures. Accepted in Appl. Phys. Lett. (2008

Single Stranded DNA Induced Assembly of Gold Nanoparticles

The binding affinity of single stranded DNA (ssDNA) for gold nanoparticle surface is studied in this work. The data indicate that the strength of interaction between ssDNA and Au particle surface is closely related to the particle size, with smaller particles (5 nm) producing the most pronounced effects. From these experimental findings, a single stranded DNA (ssDNA) based method to assimilate 13 and 5 nm gold nanoparticles was developed, and verified by transmission electron microscopy (TEM).Singapore-MIT Alliance (SMA

Electrochemical Insertion/extraction of Lithium in Multiwall Carbon Nanotube/Sb and SnSb₀.₅ Nanocomposites

Multiwall carbon nanotubes (CNTs) were synthesized by catalytic chemical vapor deposition of acetylene and used as templates to prepare CNT-Sb and CNT-SnSb₀.₅ nanocomposites via the chemical reduction of SnCl₂ and SbCl₃ precursors. SEM and TEM imagings show that the Sb and SnSb₀.₅ particles were uniformly dispersed in the CNT web and on the outside surface of CNTs. These CNT-metal composites are active anode materials for lithium ion batteries, showing improved cyclability compared to unsupported Sb and SnSb particles; and higher reversible specific capacities than CNTs. The improvement in cyclability may be attributed to the nanoscale dimensions of the metal particles and CNT’s role as a buffer in containing the mechanical stress arising from the volume changes in electrochemical lithium insertion and extraction reactions.Singapore-MIT Alliance (SMA

Tubular Organization of SnO2 Nanocrystallites for Improved Lithium Ion Battery Anode Performace

Porous tin oxide nanotubes were obtained by vacuum infiltration of tin oxide nanoparticles into porous aluminum oxide membranes, followed by calcination. The porous tin oxide nanotube arrays so prepared were characterized by FE-SEM, TEM, HRTEM, and XRD. The nanotubes are open-ended, highly ordered with uniform cross-sections, diameters and wall thickness. The tin oxide nanotubes were evaluated as a substitute anode material for the lithium ion batteries. The tin oxide nanotube anode could be charged and discharged repeatedly, retaining a specific capacity of 525 mAh/g after 80 cycles. This capacity is significantly higher than the theoretical capacity of commercial graphite anode (372 mAh/g) and the cyclability is outstanding for a tin based electrode. The cyclability and capacities of the tin oxide nanotubes were also higher than their building blocks of solid tin oxide nanoparticles. A few factors accounting for the good cycling performance and high capacity of tin oxide nanotubes are suggested.Singapore-MIT Alliance (SMA

Biological Routes to Gold Nanoplates

Much effort has been devoted to the synthesis of gold nanoparticles with different shapes, including the zero-dimensional nanospheres, one dimensional nanorods, and two-dimensional nanoplates. Compared to zero or one dimensional nanostructures, the synthesis of two-dimensional nanostructures in high yield has always been more involved, often requiring complex and time-consuming steps such as morphology transformation from the nanospheres, or the seeded growth process. Herein we report a high yield method for gold nanoplate synthesis using the extract of unicellular green alga Chlorella vulgaris, which can be carried out under ambient conditions. More than 90% of the total nanoparticle population is of the platelet morphology, surpassing the previously reported value of 45%. The control of the anisotropic growth of different planes; as well as the lateral size, has also been partially optimized.Singapore-MIT Alliance (SMA

Preparation of PtNi Nanoparticles for the Electrocatalytic Oxidation of Methanol

Carbon supported PtNi nanoparticles were prepared by hydrazine reduction of Pt and Ni precursor salts under different conditions, namely by conventional heating (PtNi-1), by prolonged reaction at room temperature (PtNi-2) and by microwave assisted reduction (PtNi-3). The nanocomposites were characterized by XRD, EDX, XPS and TEM and used as electrocatalysts in direct methanol fuel cell (DMFC) reactions. Investigations into the mechanism of PtNi nanoparticle formation revealed that platinum nanoparticle seeding was essential for the formation of the bimetallic nanoparticles. The average particle size of PtNi prepared by microwave irradiation was the lowest, in the range of 2.9 – 5.8 nm. The relative rates of electrooxidation of methanol at room temperature as measured by cyclic voltammetry showed an inverse relationship between catalytic activity and particle size in the following order PtNi-1 < PtNi-2 < PtNi-3.Singapore-MIT Alliance (SMA

Template Synthesis of Tubular Sn-Based Nanostructures for Lithium Ion Storage

We report herewith the preparation of SnO₂ nanotubes with very good shape and size control, and with and without a carbon nanotube overlayer, The SnO₂-core/carbon-shell nanotubes are excellent reversible Li ion storage compounds combining the best features of carbon (cyclability) and SnO₂ (capacity) to deliver a high specific capacity (~540-600 mAh/g) simultaneous with good cyclability (0.0375% capacity loss per cycle).Singapore-MIT Alliance (SMA

Preparation of DNA-Functionalised CdSe/ZnS Quantum Dots

We functionalised core-shell CdSe/ZnS quantum dots (QDots) with short-chain 3-mercaptopropionic acid (3MPA) to render these nanocrystalline semiconductor water-soluble. The ligand-exchange reaction was significantly improved with the use of an organic base to first remove the thiolic hydrogen. Non-bound 3MPA could be removed from the colloid by dialysis, but it was found that the choice of membrane is important. Cellulose membrane obliterated the photoluminescence of the QDots, while cellulose-acetate membrane worked well. Amine-modified DNA was then attached to the QDots through amide bond linkage, using EDC and NHS as reaction promoters. The pH of the reaction medium has an important impact on the successful attachment of functional DNA on the QDots.Singapore-MIT Alliance (SMA

A Computational Study to Understand the Surface Reactivity of Gold Nanoparticles with Amines and DNA

We conducted a computational adsorption study of methylamine on various surface-models of gold nanoparticle which is facetted by multiple {111} and {100} planes. In addition to these flat surfaces, our models include the stepped surfaces (ridges) formed along the intersections of these planes. Binding on the flat surface was fairly weak, but substantially stronger on the ridges by an average of 4.4 kcal/mol. This finding supports the idea that ssDNA’s interaction with gold nanoparticles occurs through the amines on the purine/pyrrimidine rings. Also, this typically undesirable interaction between DNA and gold nanoparticles is expected to increase as the particle size decreases. Our analysis suggests that particle size is an important controlling parameter to reduce this interaction.Singapore-MIT Alliance (SMA

Simple and Versatile Route to the Synthesis of Anisotropic Bimetallic Core-Shell and Monometallic Hollow Nanostructures: Ag (AgCl)-Pt Core-Shell Nanocubes and Pt Nanoboxes

We report herewith a simple and versatile route for the preparation of anisotropic Ag(AgCl)-Pt core-shell nanocubes and Pt nanoboxes. The core-shell nanocubes were first synthesized through the simultaneous reduction method and then treated with bis-(p-sulfonatophenyl)-phenylphosphine (BSPP) to remove the core materials. The changes in morphology, structure and composition during these syntheses were carefully followed. We found that, BSPP, in addition to being an effective silver oxidant, is also a good solubilizer for AgCl nanoparticles at room temperature. This allowed us to prepare pure Pt nanoboxes easily from the as-synthesized Ag (AgCl)-Pt nanocubes using a greatly simplified post-treatment for AgCl, which is the perennial impurity byproduct in the preparation of hollow nanostructures by the replacement reactions.Singapore-MIT Alliance (SMA