Strain-Induced Hierarchy of Energy Levels in CdS/ZnS Nanocrystals

Aside of size and shape, the strain induced by the mismatch of lattice parameters between core and shell in the nanocrystalline regime is an additional degree of freedom to engineer the electron energy levels. Herein, CdS/ZnS core/shell nanocrystals (NCs) with shell thickness up to four monolayers are studied. As a manifestation of strain, the low temperature radiative lifetime measurements indicate a reduction in Stokes shift from 36 meV for CdS to 5 meV for CdS/ZnS with four monolayers of overcoating. Concomitant crossover of S- and P-symmetric hole levels is observed which can be understood in the framework of theoretical calculations predicting flipping the hierarchy of ground hole state by the strain in CdS NCs. Furthermore, a nonmonotonic variation of higher energy levels in strained CdS NCs is discussed.

Hydrogen energy future with formic acid: a renewable chemical hydrogen storage system

Formic acid, the simplest carboxylic acid, is found in nature or can be easily synthesized in the laboratory (major by-product of some second generation biorefinery processes); it is also an important chemical due to its myriad applications in pharmaceuticals and industry. In recent years, formic acid has been used as an important fuel either without reformation (in direct formic acid fuel cells, DFAFCs) or with reformation (as a potential chemical hydrogen storage material). Owing to the better efficiency of DFAFCs compared to several other PEMFCs and reversible hydrogen storage systems, formic acid could serve as one of the better fuels for portable devices, vehicles and other energy-related applications in the future. This perspective is focused on recent developments in the use of formic acid as a reversible source for hydrogen storage. Recent developments in this direction will likely give access to a variety of low-cost and highly efficient rechargeable hydrogen fuel cells within the next few years by the use of suitable homogeneous metal complex/heterogeneous metal nanoparticle-based catalysts under ambient reaction conditions. The production of formic acid from atmospheric CO2 (a greenhouse gas) will decrease the CO2 content and may be helpful in reducing global warming.

Fluoranthene derivatives as blue fluorescent materials for non-doped organic light-emitting diodes

In this study, we report synthesis of symmetrically and non-symmetrically functionalized fluoranthene-based blue fluorescent molecular materials for non-doped electroluminescent devices. The solid state structure of these fluorophores has been established by single crystal X-ray diffraction analysis. Furthermore, a detailed experimental and theoretical study has been performed to understand the effect of substitution of symmetric and non-symmetric functional groups on optical, thermal and electrochemical properties of fluoranthene. These materials exhibit a deep blue emission and high PLQY in solution and solid state. The vacuum deposited, non-doped electroluminescent devices with the device structure ITO/NPD (15 nm)/CBP (15 nm)/EML (40 nm)/TPBI (30 nm)/LiF (1 nm)/Al were fabricated and characterized. A systematic shift in the peak position of EL emission was observed from sky blue to bluish-green with EL maxima from 477 nm to 490 nm due to different functional groups on the periphery of fluoranthene. In addition, a high luminance of >= 2000 cd m(-2) and encouraging external quantum efficiency (EQE) of 1.1-1.4% were achieved. A correlation of the molecular structure with device performance has been established.

Physical insights into salicylic acid release from poly(anhydrides)

Salicylic acid (SA) based biodegradable polyanhydrides (PAHs) are of great interest for drug delivery in a variety of diseases and disorders owing to the multi-utility of SA. There is a need for the design of SA-based PAHs for tunable drug release, optimized for the treatment of different diseases. In this study, we devised a simple strategy for tuning the release properties and erosion kinetics of a family of PAHs. PAHs incorporating SA were derived from related aliphatic diacids, varying only in the chain length, and prepared by simple melt condensation polymerization. Upon hydrolysis induced erosion, the polymer degrades into cytocompatible products, including the incorporated bioactive SA and diacid. The degradation follows first order kinetics with the rate constant varying by nearly 25 times between the PAH obtained with adipic acid and that with dodecanedioic acid. The release profiles have been tailored from 100% to 50% SA release in 7 days across the different PAHs. The release rate constants of these semi-crystalline, surface eroding PAHs decreased almost linearly with an increase in the diacid chain length, and varied by nearly 40 times between adipic acid and dodecanedioic acid PAH. The degradation products with SA concentration in the range of 30-350 ppm were used to assess cytocompatibility and showed no cytotoxicity to HeLa cells. This particular strategy is expected to (a) enable synthesis of application specific PAHs with tunable erosion and release profiles; (b) encompass a large number of drugs that may be incorporated into the PAH matrix. Such a strategy can potentially be extended to the controlled release of other drugs that may be incorporated into the PAH backbone and has important implications for the rational design of drug eluting bioactive polymers.

Low Threshold Quantum Dot Lasers

Semiconductor quantum dots have replaced conventional inorganic phosphors in numerous applications. Despite their overall successes as emitters, their impact as laser materials has been severely limited. Eliciting stimulated emission from quantum dots requires excitation by intense short pulses of light typically generated using other lasers. In this Letter, we develop a new class of quantum dots that exhibit gain under conditions of extremely low levels of continuous wave illumination. We observe thresholds as low as 74 mW/cm(2) in lasers made from these materials. Due to their strong optical absorption as well as low lasing threshold, these materials could possibly convert light from diffuse, polychromatic sources into a laser beam.

SiO2 对Bi2O3-B2O3 玻璃体系光学、热学及结构的 影响

Glasses with compositions 50Bi2O3-xB2O3- (50-x)SiO2(x=0, 10, 20, 30, 40, 50) in mol% have been prepared by using a normal melt-quench technique. The effect of SiO2 addition on thermal stability, optical properties and structural characteristic on Bi2O3-B2O3 glass were systematically investigated by using XRD, DTA, ultraviolet-visible transmittance spectra, midinfrared transmittance spectra and Raman spectra. The experimental results demonstrate that, with the addition of SiO2, thermal stability of glass samples has been obviously improved. Once the amount of SiO2 is too much, the glass samples tend to be phase seperation which results in the decrease of thermal stability. With increasing SiO2 content, the UV cutoff edge firstly shifts to short-wave band and then shifts to long-wave band, and the transmittance of mid-infrared has been greatly improved. With substitution of SiO2 for B2O3, the [BO3] triangles and [BO4] tetrahedral groups are gradually replaced by [SiO4]. [BiO6] octahedral and [SiO4] tetrahedral units are connected forming a vibrational mode of Bi-O-Si. The physical chemistry and optical performance of Bi2O3-B2O3 glass were greatly improved by addition of SiO2.

Optimized vertical carbon nanotube forests for multiplex surface-enhanced raman scattering detection

The highly sensitive and molecule-specific technique of surface-enhanced Raman spectroscopy (SERS) generates high signal enhancements via localized optical fields on nanoscale metallic materials, which can be tuned by manipulation of the surface roughness and architecture on the submicrometer level. We investigate gold-functionalized vertically aligned carbon nanotube forests (VACNTs) as low-cost straightforward SERS nanoplatforms. We find that their SERS enhancements depend on their diameter and density, which are systematically optimized for their performance. Modeling of the VACNT-based SERS substrates confirms consistent dependence on structural parameters as observed experimentally. The created nanostructures span over large substrate areas, are readily configurable, and yield uniform and reproducible SERS enhancement factors. Further fabricated micropatterned VACNTs platforms are shown to deliver multiplexed SERS detection. The unique properties of CNTs, which can be synergistically utilized in VACNT-based substrates and patterned arrays, can thus provide new generation platforms for SERS detection. © 2012 American Chemical Society.

Self-assembled multilayer graphene oxide membrane and carbon nanotubes synthesized using a rare form of natural graphite

The fabrication of flexible multilayer graphene oxide (GO) membrane and carbon nanotubes (CNTs) using a rare form of high-purity natural graphite, vein graphite, is reported for the first time. Graphite oxide is synthesized using vein graphite following Hummer's method. By facilitating functionalized graphene sheets in graphite oxide to self-assemble, a multilayer GO membrane is fabricated. Electric arc discharge is used to synthesis CNTs from vein graphite. Both multilayer GO membrane and CNTs are investigated using microscopy and spectroscopy experiments, i.e., scanning electron microscopy (SEM), atomic force microscopy (AFM), high-resolution transmission electron microscopy (HRTEM), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), thermogravimetric analysis (TGA), core level photoelectron spectroscopy, and C K-edge X-ray absorption spectroscopy (NEXAFS), to characterize their structural and topographical properties. Characterization of vein graphite using different techniques reveals that it has a large number of crystallites, hence the large number of graphene sheets per crystallite, preferentially oriented along the (002) plane. NEXAFS and core level spectra confirm that vein graphite is highly crystalline and pure. Fourier transform infrared (FT-IR) and C 1s core level spectra show that oxygen functionalities (-C-OH, -CO,-C-O-C-) are introduced into the basal plane of graphite following chemical oxidation. Carbon nanotubes are produced from vein graphite through arc discharge without the use of any catalyst. HRTEM confirm that multiwalled carbon nanotube (MWNTs) are produced with the presence of some structure in the central pipe. A small percentage of single-walled nanotubes (SWNTs) are also produced simultaneously with MWNTs. Spectroscopic and microscopic data are further discussed here with a view to using vein graphite as the source material for the synthesis of carbon nanomaterials. © 2013 American Chemical Society.

Segmented All-Platinum Nanowires with Controlled Morphology through Manipulation of the Local Electrolyte Distribution in Fluidic Nanochannels during Electrodeposition

Synthesis of segmented all-Pt nanowires is achieved by a template-assisted method. The combination of a suitably chosen electrolyte/template system with pulse-reverse electrodeposition allows the formation of well-defined segments linked to nanowires. Manipulation of the morphology is obtained by controlling the electrokinetie effects on the local electrolyte distribution inside the nanochannels during the nanowire growth process, allowing a deviation from the continuously cylindrical geometry given by the nanoporous template. The length of the segments can be adjusted as a function of the cathodic pulse duration. Applying constant pulses leads to segments with homogeneous shape and dimensions along most of the total wire length. X-ray diffraction demonstrates that the preferred crystallite orientation of the polycrystalline wires varies with the average segment length. The results are explained considering transitions in texture formation with increasing thickness of the electrodeposit. A mechanism of segment formation is proposed based on structural characterizations. Nanowires with controlled segmented morphology are of great technological importance, because of the possibility to precisely control their substructure as a means of tuning their electrical, thermal, and optical properties. The concept we present in this work for electrodeposited platinum and track-etched polycarbonate membranes can be applied to other selected materials as well as templates and constitutes a general method to controlled nanostructuring and synthesis of shape controlled nanostructures.

Phase transformation in the surface region of zirconia and doped zirconia detected by UV Raman spectroscopy

The phase evolution of yttrium oxide and lanthanum oxide doped zirconia (Y2O3-ZrO2 and La2O3-ZrO2, respectively) from their tetragonal to monoclinic phase has been studied using UV Raman spectroscopy, visible Raman spectroscopy and XRD. UV Raman spectroscopy is found to be more sensitive at the surface region while visible Raman spectroscopy and XRD mainly give the bulk information. For Y2O3-ZrO2 and La2O3-ZrO2, the transformation of the bulk phase from the tetragonal to the monoclinic is significantly retarded by the presence of yttrium oxide and lanthanum oxide. However, the tetragonal phase in the surface region is difficult to stabilize, particularly when the stabilizer's content is low. The phase in the surface region can be more effectively stabilized by lanthanum oxide than yttrium oxide even though zirconia seemed to provide more enrichment in the surface region of the La2O3-ZrO2 sample than the Y2O3-ZrO2 sample, based on XPS analysis. The surface structural tension and the enrichment of the ZrO2, component in the surface region of ZrO2-Y2O3 and ZrO2-La2O3 might be the reasons for the striking difference between the phase change in the surface region and the bulk. Accordingly, the stabilized tetragonal surface region can significantly prevent the phase transition from developing into the bulk when the stabilizer's content is high.

Preparation and characterization of multiwalled carbon nanotube-supported platinum for cathode catalysts of direct methanol fuel cells

Multiwalled carbon nanotube-supported Pt (Pt/MWNT) nanocomposites were prepared by both the aqueous solution reduction of a Pt salt (HCHO reduction) and the reduction of a Pt ion salt in ethylene glycol solution. For comparison, a Pt/XC-72 nanocomposite was also prepared by the EG method. The Pt/MWNT catalyst prepared by the EG method has a high and homogeneous dispersion of spherical Pt metal particles with a narrow particle-size distribution. TEM images show that the Pt particle size is in the range of 2-5 nm with a peak at 2.6 nm, which is consistent with 2.5 nm obtained from the XRD broadening calculation. Surface chemical modifications of MWNTs and water content in EG solvent are found to be the key factors in depositing Pt particles on MWNTs. In the case of the direct methanol fuel cell (DMFC) test, the Pt/MWNT catalyst prepared by EG reduction is slightly superior to the catalyst prepared by aqueous reduction and displays significantly higher performance than the Pt/XC-72 catalyst. These differences in catalytic performance between the MWNT-supported or the carbon black XC-72-supported catalysts are attributed to a greater dispersion of the supported Pt particles when the EG method is used, in contrast to aqueous HCHO reduction and to possible unique structural and higher electrical properties when contrasting MWNTs to carbon black XC-72 as a support.

Bonding and correlation analysis of various SiCO isomers

The structural properties for various SiCO isomers in the singlet and triplet states have been investigated using CASSCF methods with a 6-311 +G* basis set and also using three DFT and MP2 with same basis set for those systems except for the linear singlet state. The detailed bonding character is discussed, and the state-state correlations and the isomerization mechanism are also determined. Results indicate that there are four different isomers for each spin state, and for all isomers, the triplet state is more stable than the corresponding singlet state. The most stable is the linear SiCO ((3)Sigma(-)) species and may be refer-red to the ground state. At the CASSCF-MP2(full)/6-311+G* level, the state-state energy separations of the other triplet states relative to the ground state are 43.2 (cyclic), 45.2 (linear SiOC), and 75.6 kcal/mol (linear CSiO), respectively, whereas the triplet-singlet state excitation energies for each configuration are 17.3 (linear SiCO), 2.2 (cyclic SiCO), 10.2 (linear SiOC), and 18.5 kcal/mol (linear CSiO), respectively. SiCo ((3)Sigma(-)) may be classified as silene (carbonylsilene), and its COdelta- moiety possesses CO- property. The dissociation energy of the ground state is 42.5 kcal/mol at the CASSCF-MP2(full)/6-311+G* level and falls within a range of 36.5-41.5 kcal/mol at DFT level, and of 23.7-28.9 kcal/mol at the wave function-correlated level, whereas the vertical IP is 188.8 kcal/mol at the CASSCF-MP2(full)/6-311+G* level and is very close to the first IP of Si atom. Three linear isomers (SiCO, SiOC, and CSiO) have similar structural bonding character. SiOC may be referred to the iso-carbonyl Si instead of the aether compound, whereas the CSiO isomer may be considered as the combination of C (the analogue of Si) with SiO (the analogue of CO). The bonding is weak for all linear species, and the corresponding potential energy surfaces are flat, and thus these linear molecules are facile. Another important isomer is of cyclic structure, it may be considered as the combination of CO with Si by the side pi bond. This structure has the smallest triplet state-singlet state excitation energy (similar to2.2 kcal/mol); the C-O bonds are longer, and the corresponding vibrational frequencies are significantly smaller than those of the other linear species. This cyclic species is not classified as an epoxy compound. State-state correlation analysis and the isomerization pathway searches have indicated that there are no direct correlations among three linear structures for each spin state, but they may interchange by experiencing two transition states and one cyclic intermediate. The easiest pathway is to break the Si-O bond to go to the linear SiCO, but its inverse process is very difficult. The most difficult process is to break the C-O bond and to go to the linear CSiO.

Energy-Level and Molecular Engineering of Organic D-pi-A Sensitizers in Dye-Sensitized Solar Cells

A series of organic D-pi-A sensitizers composed of different triarylamine donors in conjugation with the thienothiophene unit and cyanoacrylic acid as an acceptor has been synthesized at a moderate yield. Through tuning the number of methoxy substituents on the triphenylamine donor, we have gradually red-shifted the absorption of sensitizers to enhance device efficiencies.