Quantum-dot-sensitized TiO2 inverse opals for photoelectrochemical hydrogen generation.

A new nanoarchitecture photoelectrode design comprising CdS quantum-dot-sensitized, optically and electrically active TiO(2) inverse opals is developed for photoelectrochemical water splitting. The photoelectrochemical performance shows high photocurrent density (4.84 mA cm(-2) at 0 V vs. Ag/AgCl) under simulated solar-light illumination.

High hardness BaCb-(BxOy/BN) composites with 3D mesh-like fine grain-boundary structure by reactive spark plasma sintering.

Boron carbide B4C powders were subject to reactive spark plasma sintering (also known as field assisted sintering, pulsed current sintering or plasma assisted sintering) under nitrogen atmosphere. For an optimum hexagonal BN (h-BN) content estimated from X-ray diffraction measurements at approximately 0.4 wt%, the as-prepared BaCb-(BxOy/BN) ceramic shows values of Berkovich and Vickers hardness of 56.7 +/- 3.1 GPa and 39.3 +/- 7.6 GPa, respectively. These values are higher than for the vacuum SPS processed B4C pristine sample and the h-BN -mechanically-added samples. XRD and electronic microscopy data suggest that in the samples produced by reactive SPS in N2 atmosphere, and containing an estimated amount of 0.3-1.5% h-BN, the crystallite size of the boron carbide grains is decreasing with the increasing amount of N2, while for the newly formed lamellar h-BN the crystallite size is almost constant (approximately 30-50 nm). BN is located at the grain boundaries between the boron carbide grains and it is wrapped and intercalated by a thin layer of boron oxide. BxOy/BN forms a fine and continuous 3D mesh-like structure that is a possible reason for good mechanical properties.

Non-catalytic facile synthesis of superhard phase of boron carbide (B13C2) nanoflakes and nanoparticles.

Boron Carbide is one the hardest and lightest material that is also relatively easier to synthesis as compared to other superhard ceramics like cubic boron nitride and diamond. However, the brittle nature of monolithic advanced ceramics material hinders its use in various engineering applications. Thus, strategies that can toughen the material are of fundamental and technological importance. One approach is to use nanostructure materials as building blocks, and organize them into a complex hierarchical structure, which could potentially enhance its mechanical properties to exceed that of the monolithic form. In this paper, we demonstrated a simple approach to synthesize one- and two-dimension nanostructure boron carbide by simply changing the mixing ratio of the initial compound to influence the saturation condition of the process at a relatively low temperature of 1500 degrees C with no catalyst involved in the growing process. Characterization of the resulting nano-structures shows B13C2, which is a superhard phase of boron carbide as its hardness is almost twice as hard as the commonly known B4C. Using ab-initio density functional theory study on the elastic properties of both B12C3 and B13C2, the high hardness of B13C2 is consistent to our calculation results, where bulk modulus of B13C2 is higher than that of B4C. High resolution transmission electron microscopy of the nanoflakes also reveals high density of twinning defects which could potentially inhibit the crack propagation, leading to toughening of the materials.

3-Dimensional photonic crystal surface enhanced upconversion emission for improved near-infrared photoresponse.

The enhancement of upconversion luminescence of lanthanide-ion doped fluoride upconversion nanoparticles (UCNPs) is particularly important and highly required for their myriad applications in sensing, photoelectronic devices and bio-imaging. In this work, the amplification of luminescence in NaYF4:Yb/Er and NaYF4:Yb/Tm UCNPs in close proximity to the three-dimensional photonic crystal (3D PC) surface for improved near-infrared photoresponse of a carbon nanotube-based phototransistor is reported. The self-assembled opal 3D PCs with polystyrene sphere sizes of 200, 290 and 360 nm that exhibit reflection peaks of 450, 650 and 800 nm respectively were used for upconversion enhancement, and around 30 times enhancement was obtained for NaYF4:Yb/Er and NaYF4:Yb/Tm UCNPs. Time-resolved upconversion emission and 3D PC transmittance-dependent upconversion enhancement reveal that the enhanced absorption and the extraction effects, resulting from the enhanced non-resonant pump excitation field and the strong coherent scattering provided by 3D PCs respectively, are responsible for the large enhancement. As a proof-of-concept experiment, the prepared 3D PC/NaYF4:Yb/Tm UCNP coupled material layer was introduced into the carbon nanotube-based phototransistor. It is shown that the photoresponsivity of the device to near-infrared light was improved by 10 times with respect to the control device with carbon nanotubes only, which reveals the promising applications of this coupled material in photoelectronic devices such as photovoltaics and other types of phototransistors.

Multicolor tunability and upconversion enhancement of fluoride nanoparticles by oxygen dopant.

The ability to manipulate the upconversion luminescence of lanthanide-ion doped fluoride upconversion nanoparticles (UCNPs) is particularly important and highly desired due to their wide applications in color displays, multiplexing bioassays and multicolor imaging. Here, we developed a strategy for simultaneously tuning color output and enhancing upconversion emission of Yb/Er doped fluoride UCNPs, based on adjusting the oxygen doping level. The synthesis of multicolored multifunctional NaGdF4:Yb,Er UCNPs was used as the model host system to demonstrate this protocol. Ammonium nitrate (NH4NO3) was used as the oxygen source and added into the reaction system at the beginning stage of nucleation and growth process of fluoride UCNPs, which facilitates the formation of enough oxygen atoms and the diffusion of these into the fluoride host matrix. The results revealed that multicolour output and upconversion enhancement mainly resulted from the variation of phonon energy and crystal field symmetry of the host lattice, respectively. This strategy can be further expanded to other fluoride host matrices. As an example of an application, multicolored UCNPs were used as a color converter in light emitting diodes, which can effectively convert near-infrared light into visible light. It is expected that these multicolored UCNPs will be promising for applications in multiplexing biodetection, bioimaging (optical and magnetic resonance imaging) and other optical technologies, and the present method for the control of O(2-) doping may also be used in other functional nanomaterials.

Photon upconversion in hetero-nanostructured photoanodes for enhanced near-infrared light harvesting.

A hetero-nanostructured photoanode with enhanced near-infrared light harvesting is developed for photo-electrochemical cells. By spatially coating upconversion nanoparticles and quantum dot photosensitizers onto TiO2 inverse opal, this architecture allows direct irradiation of upconversion nanoparticles to emit visible light that excites quantum dots for charge separation. Electrons are injected into TiO2 with minimal carrier losses due to continuous electron conducting interface.

Homogeneous photosensitization of complex TiO2 nanostructures for efficient solar energy conversion.

TiO2 nanostructures-based photoelectrochemical (PEC) cells are under worldwide attentions as the method to generate clean energy. For these devices, narrow-bandgap semiconductor photosensitizers such as CdS and CdSe are commonly used to couple with TiO2 in order to harvest the visible sunlight and to enhance the conversion efficiency. Conventional methods for depositing the photosensitizers on TiO2 such as dip coating, electrochemical deposition and chemical-vapor-deposition suffer from poor control in thickness and uniformity, and correspond to low photocurrent levels. Here we demonstrate a new method based on atomic layer deposition and ion exchange reaction (ALDIER) to achieve a highly controllable and homogeneous coating of sensitizer particles on arbitrary TiO2 substrates. PEC tests made to CdSe-sensitized TiO2 inverse opal photoanodes result in a drastically improved photocurrent level, up to ~15.7 mA/cm² at zero bias (vs Ag/AgCl), more than double that by conventional techniques such as successive ionic layer adsorption and reaction.