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This review focuses on recent developments in the study of hydrogen generation from water splitting using photoelectrochemical (PEC) cells based on metal oxide (MO) nanomaterials. The emphasis is on the unique properties of MO nanostructures and their advantages as well as limitations for PEC solar hydrogen generation. While abundant and stable, metal oxide nanomaterials tend to have weak visible light absorption that limits their use for solar energy conversion. In addition, MO nanomaterials tend to exhibit a high density of trap states or defect sites that limit their overall efficiency. Different strategies have been developed to enhance visible light absorption (e.g., doping, dye, or quantum dot sensitization and band structure engineering using composite structures) as well as to enhance transport by reducing the density of trap states via surface modification, improving crystallinity, or using 1D structures. In some cases, combining different strategies has led to strong synergistic effects. Recent studies point to the importance and promise of engineering electronic band structure for improving PEC performance of MO nanostructures for hydrogen generation and other potential applications.
A magnetic refrigeration test was performed using a test device filled with spherical GdN material synthesized by the hot isostatic pressing (HIP) method. Refrigeration with an active magnetic regenerator cycle was tested in the temperature range between 48 and 66 K, with the field changing from 1.2 to 3.7 T and 2.0 to 4.0 T at upper and lower sides of the regenerator bed filled with the GdN spheres, respectively. Temperature spans about of 2 K were obtained at both sides, and the total temperature span in each cycle attained about 5 K. The specific heat of the material was measured to calculate the magnetic entropy change ΔS and the adiabatic temperature change ΔT induced by the magnetic field change ΔH. It was suggested that for a given ΔH, larger ΔS and ΔT can be exploited when demagnetized to lower H, especially, to zero field.
Fluorescent nanodiamonds (FNDs) with a size in the range of 10 – 100 nm have been produced by ion irradiation and annealing, and isolated by differential centrifugation. Single particle spectroscopic characterization with confocal fluorescence microscopy and fluorescence correlation spectroscopy indicates that they are photostable and useful as an alternative to far-red fluorescent proteins for bioimaging applications. We demonstrate the application by performing in vivo imaging of bare and bioconjugated FND particles (100 nm in diameter) in C. elegans and zebrafishes and exploring the interactions between this novel nanomaterial and the model organisms. Our results indicate that FNDs can be delivered to the embryos of both organisms by microinjection and eventually into the hatched larvae in the next generation. No deleterious effects have been observed for the carbon-based nanoparticles in vivo. The high fluorescence brightness, excellent photostability, and nontoxic nature of the nanomaterial have allowed long-term imaging and tracking of embryogenesis in the organisms.
Since their re-introduction as new generation solar cells in 1991,dye-sensitized solar cells (DSSCs) have been studied extensively to improvetheir efficiency and their stability. Few papers have reported the usage ofnatural dyes in the fabrication of DSSCs. We are most interested in thesedyes being easy to extract, low cost and with tunable absorption. Forexample, Anthocyanin is extracted from red cabbage and is present in amultitude of colors ranging from red to yellow to violet according to thepH. In this study, two industrial types of titanium dioxide powders, theDegussa P 25 and the Crystal 128 with different particle sizes 21 and 200 nmrespectively, were used to prepare DSSCs. The dye used is anthocyanin andits color is varied by varying the pH of the medium. The pH effect on thelight absorption of anthocyanin in the visible range and the opticalproperties of titanium dioxide dyed with anthocyanin and coumarin 102 areinvestigated using UV-Vis spectroscopy. The open-circuit voltage of all thesamples is tested and it if found out that it is dependant on the dyecolor.
Three families of NixZry (x = 28, 36, 38, x + y = 100%) metallic glasses were prepared and examined using X-ray, temperature dependent transport and magnetic field. X-ray characterization shows characteristic diffuse spectrum, except for narrow regions of control samples, where partial crystallization was induced in finite small volumes. Magnetic properties confirm spin-fluctuating paramagnetic-like behavior, which we asses from preliminary Hall coefficient measurements, which is quantitatively different in three sample families. Temperature dependent AC and DC transport measurements were conducted in a broad temperature range from 70 K to 700 K, finding both quantitative and semi-qualitative differences between samples with different Ni/Zr ratio.
We present in this text a new experimental tool to study the mixing of atoms under irradiation. Based on physics of x ray diffraction, the specular reflectivy of x ray was used to estimate the Auto Correlation Function associated with the electron density gradient. The accuracy of the ACF is around 1 nanometer and does not evolve with the thickness of the probed layer. Thus, this point allows accurately measuring the broadening of the electron density gradient spreading induced by irradiation. Such an accurate profile extracted over a large range of fluences (about 3 decades) would lead to the determination of the functional dependence of this spreading with the fluence. This could allow pointing out the main mechanisms triggering the atomic mixing over large distances when atomic mixing occurring in thermal spikes is washed out.
The Si nanocrystal-films are prepared by pulsed laser ablation of Si target in a mixture of helium and hydrogen gas. The total gas pressure and hydrogen partial gas pressure were varied to control structure of nanocrystal-film. The surface of Si nanocrystallite was hydrogenated and degree of hydrogenation increased with increasing hydrogen partial gas pressure. The aggregate structure of nanocrystal-film depended on both the total gas pressure and the hydrogen partial gas pressure. The former and the latter alter spatial confinement of Si species during deposition and the surface hydrogenation of individual nanocrystal, respectively. Spatial confinement increases probability of collision between nanocrystals in the plume. While, surface hydrogenation prevents coalescence of nanocrystals. The individual or aggregated nanocrystals formed in the plume reach the substrate and the nanocrystal-film is deposited on the substrate. The non-equilibrium growth processes during pulsed laser ablation are essential for the formation of the surface structure and the subsequent nanocrystal-film growth. Our results indicate that the structure of nanocrystal-film depends on the probabilities of collision and coalescence between nanocrystals in the plume. These probabilities can be varied by controlling the total gas pressure and the hydrogen partial gas pressure.
We have conjugated chloroquine onto nano-sized, thiol-stabilized gold nanoparticles by using 1-ethyl-3-[3-dimethylaminopropyl] carbodiimide hydrochloride (EDC) / N-hydroxysulfosuccinimide (NHS) chemistry. The formation of gold nanoparticles was confirmed using optical spectra for characteristic surface plasmon band; the average size of gold nanoparticles was found to be 5-7 nm from electron microscopy measurements. The anti-tumor activity of prepared nanocomposite, vis-à-vis chloroquine itself, had been demonstrated using MCF-7 breast cancer cell line. To determine the binding affinity of gold-chloroquine nanocomposites to transport proteins present in blood serum, we studied the binding interaction of gold-chloroquine to bovine serum albumin (BSA), the most abundant plasma protein. The binding was studied by using isothermal titration calorimetry and fluorescence spectroscopy and was analyzed in terms of binding constant, entropy and enthalpy change. The gold-chloroquine nanocomposites were found to interact efficiently with BSA and fluorescence quenching experiments involving Trp212 suggests that the nanocomposites bind at site I of BSA.
In this work a series of Eosin Y-ZnO(x%)/TiO2 were prepared. ZnO well dispersed on the surface of TiO2, which improves the adsorption of Eosin Y and the excited electron to transfer to the conduction band of TiO2. Therefore the visible light activity of 0.2%Pt-Eosin Y-ZnO(x%)/TiO2 is much higher than that of the 0.2%Pt-Eosin Y-TiO2 and 0.2%Pt-Eosin Y-ZnO. The 0.2%Pt-Eosin Y- ZnO(1.5%)/TiO2 has the highest visible light activity among the catalysts coupled with various ZnO amount, whose activity is increased by a factor of 3.5 compared to that of 0.2%Pt-Eosin Y-TiO2. It is proposed that, 0.2%Pt-Eosin Y-ZnO(1.5%)/TiO2 has the optimal trapping sites of carriers and thickness of the space-charge layer on the TiO2 particle surface, so these factors result a more efficient charge separation, an increased lifetime of the charge carriers, and the enhanced of hydrogen production .
This paper discusses recent progress made in developing an advanced sp2 carbon-based materials that can be produced by wet coating as a thin layer and processed to form highly ordered arrays of Graphene Nanoribbons (GNRs) that attach to the substrate on edge with their planes parallel to each other. The fabrication method is based on carbonization of organic molecules spatially preordered in crystalline film on the substrate. This material, named Ribtan, can be used to fabricate GNRs films over large areas that exhibit a very smooth film surface and can form strong covalent bonds to the substrate. The width (film thickness) of Ribtan GNRs can be controlled precisely down to a few nanometers. We demonstrated advantage of Ribtan material for application in supercapacitors as well as feasibility for use in transparent electrodes, solid tribological coatings, and thin film transistors.
Extremely high surface area porous electrodes are of interest as current collectors for advanced batteries and as the basis for supercapacitors. For moderate to large scale storage applications a three-dimensional material is needed with porosity at multiple length scales. We are developing a combined bottom up/top down approach to creating such materials by using electrodeposition of mesoporous silica on nickel foam, a commercially available porous conductor widely used as the current collector in various batteries. Electrodeposition produces a conformal coating on the nickel foam. By controlling the electrodeposition time the morphology of the mesoporous silica can be varied from a thin film up to 500 nm thick to a loosely bound agglomeration of mesoporous silica particles capable of completely filling the 0.3-0.5 mm voids of the nickel foam. The internal diameter of the mesopores in the silica can be controlled in the range 2.5-4.8 nm by changing the chain length of the templating surfactant used. Gas adsorption shows surface areas of 400-1600 m2/g of silica deposited, consistent with the assumed structure of the material.
Rosette nanotubes (RNTs) are obtained through the self-organization of biologically inspired self-complementary guanine-cytosine modules (G∧C motif) under physiological conditions. These architectures can express bioactive molecules on their surface by functionalizing the G∧C motif prior to self-assembly. As a result, RNTs are promising drug delivery vehicles for the treatment of diseases such as cancer and inflammatory disorders. Towards these studies, we have explored the toxicity and immunological response of RNTs and are now focused on understanding their cellular uptake, biological distribution and kinetics in vivo. For these investigations, we need to construct a RNT labeled with a radionuclide that can be followed in vivo by SPECT (single photon emission computed tomography) imaging. In this proceeding, we describe a twin G∧C motif that is functionalized with mercaptoacetyl triglycine (MAG3). This is a well known ligand which is able to form a stable chelate with the radionuclides 99mTc or 186/188Re. In order to develop the chemistry for this radiolabeling strategy for the RNTs, we demonstrate the chelation of the MAG3 functionalized twin-G∧C motif with cold rhenium and investigate the self-assembly properties of the complex into RNTs under aqueous conditions.
We have observed a pyroelectric effect (PE) in reactively sputtered aluminum nitride (AlN) thin films that is typically a factor of twenty greater than commercial pyroelectric materials such as triglycine sulfate (TGS). This is most likely due to an extrinsic effect since the known crystalline structures of AlN are too symmetric to allow such high values for the PE response. Preliminary annealing studies support the assumption that residual strains remaining from the AlN thin film deposition are the most likely source of the anomalously high PE response. The results of these studies are presented along with some measurements that indicate a still higher PE response might be obtainable.
We investigated the electroluminescence (EL) properties of Eu-doped GaN-based light-emitting diodes (LEDs) grown by organometallic vapor phase epitaxy (OMVPE). The thickness of the active layer was varied to increase the light output power. With increasing the active layer thickness, the light output power monotonically increased. The maximum light output power of 50 μW was obtained for an active layer thickness of 900 nm with an injected current of 20 mA, which is the highest value ever reported. The corresponding external quantum efficiency was 0.12%. The applied voltage for the LED operation also increased with the active layer thickness due to an increase in the resistance of the LED. Therefore, in terms of power efficiency, the optimized active layer thickness was around 600 nm. These results indicate that the optimization of the LED structure would effectively improve the luminescence properties.
III-Nitride based Light Emitting Diodes (LEDs) are heavily pursued for various lighting applications due to the ability to engineer the emission through the visible wavelengths by controlling the alloy composition in the multi quantum well. Planar structures are characterized by a Lambertian emission pattern, however, depending on the applications in which the LED is employed, including but not limited to, general lighting, displays, and sensors, the emission profile may need to be more or less directional. As a result, there is significant interest in both improving the efficiency and controlling the emission profile of nitride based devices. Various components such as lenses and photonic crystals are used to improve light extraction and alter the emission profile while growth on semi-polar substrates is being pursued to minimize inherent polarization effects. In this work, curved Gallium Nitride (GaN) structures have been grown utilizing growth kinetics. These as-grown features do not require the extensive additional fabrication and allow for three-dimensional substrates to be employed for LED fabrication. The details of the fabrication and the optical and electrical characterization of Indium Gallium Nitride based LEDs grown on these structures is discussed.
Control of crystal orientation of vertically grown epitaxial Si (111) and (110) nanowire arrays on Si substrate has been demonstrated using a combination of an anodic aluminum oxide (AAO) template and vapor – liquid – solid (VLS) growth method. The crystal orientation of the nanowire was investigated by transmission electron microscopy. A growth direction of the nanowire arrays was guided perpendicular to the surface of the substrate by the AAO template, and the crystal orientation of the nanowire arrays was selected using the single crystal Si substrate properly cut in desired orientation.
The study focuses on the influence of the hydrogenated amorphous silicon carbide (a-SiC:H) buffer layer in hydrogenated amorphous silicon (a-Si:H) single-junction and tandem thin-film solar cells. By increasing the undoped a-SiC:H buffer layer thickness from 6nm to 12nm, the JSC in single-junction cell was significantly improved, and the efficiency was increased by 4.5%. The buffer layer also effectively improves the efficiency of the a-Si:H/a-Si:H tandem cells by 7% as a result of the increase in open-circuit voltage (VOC) and short-circuit current (JSC). Although the bottom cell absorbs less short-wavelength photons, the wider-bandgap doped and buffer layers were still necessary for improving the cell efficiency. Presumably, this is because these wider-bandgap layers allow more photons to reach the bottom cell. Also, they can reduce interface recombination.
The study of dislocation nucleation has gained increasing attentions recently primarily due to the advancement of small scale mechanical testing methods. Based on the classic Rice model of dislocation nucleation from a crack tip in which the dislocation core is modeled by a continuous slip field, a nonlinear finite element method can be formulated with the interplanar potential as the input, and the development of interplanar slip field can be solved from the resulting boundary value problems. The effects of geometric boundary conditions, loading patterns, etc. can be conveniently determined, as opposed to the time consuming molecular simulations. To validate the method, we compare the simulations results of homogeneous dislocation nucleation and heterogeneous dislocation nucleation from a two-dimensional crack tip to the literature results. As proposed by Rice and Beltz (J. Mech. Phys. Solids, 1994), the activation energy for dislocation nucleation from a three-dimensional crack tip depends on the finite thickness in the direction parallel to the crack tip, which has been successfully reproduced in the finite element simulation results reported here.
We, as education outreach providers at a research center, believe research scientists and engineers have much to contribute to science education. Our job is to design programs that allow our faculty and students to share their expertise and their stories to positively impact student learning and attitudes towards STEM fields. Is it possible to show that middle school students’ interaction with scientists and engineers makes a positive difference in only one day? The National Science Foundation funded Princeton Center for Complex Materials (PCCM), in partnership with MRS and NOVA, held a large-scale, one-day event for middle school students on January 27, 2011. This study measures the impact of that engagement on the students’ attitudes, contributing to their general attitude towards science and scientists that will ultimately determine their career choices later in life. Among other methods, focus group interviews and pre- and post-event attitude surveys were conducted and analyzed to evaluate the impact of the program.