Harvesting Excitons Via Two Parallel Channels for Efficient White Organic LEDs with Nearly 100% Internal Quantum Efficiency: Fabrication and Emission-Mechanism Analysis

By incorporating two phosphorescent dyes, namely, iridium(III)[bis(4,6-difluorophenyl)-pyridinato-N,C-2']picolinate (Flrpic) for blue emission and bis(2-(9,9-diethyl-9H-fluoren-2-yl)-1-phenyl-1 H-benzoimidazol-N,C-3) iridium(acetylacetonate) ((fbi)(2)Ir(acac)) for orange emission, into a single-energy well-like emissive layer, an extremely high-efficiency white organic light-emitting diode (WOLED) with excellent color stability is demonstrated. This device can achieve a peak forward-viewing power efficiency of 42.5 lm W-1, corresponding to an external quantum efficiency (EQE) of 19.3% and a current efficiency of 52.8 cd A(-1). Systematic studies of the dopants, host and dopant-doped host films in terms of photophysical properties (including absorption, photoluminescence, and excitation spectra), transient photoluminescence, current density-voltage characteristics, and temperature-dependent electroluminescence spectra are subsequently performed, from which it is concluded that the emission natures of Flrpic and (fbi)(2)Ir(acac) are, respectively, host-guest energy transfer and a direct exciton formation process. These two parallel pathways serve to channel the overall excitons to both dopants, greatly reducing unfavorable energy losses.

Polyaniline/Pt Hybrid Nanofibers: High-Efficiency Nanoelectrocatalysts for Electrochemical Devices

A simple and facile procedure to synthesize a novel hybrid nanoelectrocatalyst based on polyaniline (PANI) nanofiber-supported supra-high density Pt nanoparticles (NPs) or Pt/Pd hybrid NPs without prior PANI nanofiber functionalization at room temperature is demonstrated. This represents a new type of ID hybrid nanoelectrocatalyst with several important benefits. First, the procedure is very simple and can be performed at room temperature using commercially available reagents without the need for templates and surfactants. Second, ultra-high density small "bare" Pt NPs or Pt/Pd hybrid NPs are grown directly onto the surface of the PANI nanofiber, without using any additional linker. Most importantly, the present PANI nanofiber-supported supra-high density Pt NPs or Pt/Pd hybrid NPs can be used as a signal enhancement element for constructing electrochemical devices with high performance.

Raspberry-like Hierarchical Au/Pt Nanoparticle Assembling Hollow Spheres with Nanochannels: An Advanced Nanoelectrocatalyst for the Oxygen Reduction Reaction

In this contribution, we for the first time report the synthesis of raspberry-like hierarchical Au/Pt nanoparticle (NP) assembling hollow spheres (RHAHS) with pore structure and complex morphology through one in situ sacrificial template approach without any post-treatment procedure. This method has some clear advantages including simplicity, quickness, high quality, good reproducibility, and no need of a complex post-treatment process (removing templating). Furthermore, the present method could be extended to other metal-based NP assembling hollow spheres. Most importantly, the as-prepared RHAHS exhibited excellent electrocatalytic activity for oxygen reduction reaction (ORR). For instance, the present RHAHS-modified electrode exhibited more positive potential (the half-wave potential at about 0.6 V), higher specific activity, and higher mass activity for ORR than that of commercial platinum black (CPB). Rotating ring-disk electrode (RRDE) voltarnmetry demonstrated that the RHAHS-modified electrode could almost catalyze a four-electron reduction of O-2 to H2O in a 0.5 M air-saturated H2SO4 solution.

Controlled synthesis of nanoporous Au microsheet via surfactant emulsion template

A facile and wet-chemical approach was employed to control synthesis of self-organizing, hyperbranched nanoporous Au microsheet with high quality in bulk quantity. This method produced nanoporous Au microsheets with a thickness of 7-15 nm. The microsheets were composed of irregularly interconnected planar Au nanoplates with interstices, i.e. nanopores of 10-50 nm. And the nanoporous Au microsheets were enveloped in 10-30 nm thick polyaniline (PANI) sheaths. The morphology of the nanostructured Au composites could also be easily tuned by changing the concentration of aniline and chlorauric acid. The dendritic and epitaxial growth of nanoporous Au microsheet was believed as the diffusion-limited process confined in the lamellar emulsion phase through self-assembly of aniline and dodecylsulfate. The solution reaction proceeded at a mild condition (room temperature and aqueous solutions), and less toxic reagents were employed instead of extreme toxic and corrosive chemicals.

"Green synthesis" of monodisperse Pt nanoparticles and their catalytic properties

A green synthetic strategy to prepare monodisperse Pt nanoparticles was reported. Aminodextran acted as the reductive and protective agents, and Pt nanoparticles were characterized by UV/vis spectroscopy (UV-vis), Pt nanoparticles were conveniently obtained at one step. transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FT-IR), and X-ray photoelectron spectroscopy (XPS). By changing the initial molar ratio of arninodextran to platinum precursor, Pt nanoparticles with different size were obtained. Amino groups of aminodextran could absorb on Pt nanoparticles surfaces and serve as a very good stabilizer. However, dextran without amino groups could not effectively stabilize Pt nanoparticles and aggregation of Pt nanoparticles were obtained. Catalytic activity of these Pt nanoparticles for the electron-transfer reaction between hexacyanoferrate (III) ions and thiosulfate ions was also studied, and they showed good catalytic efficiency.

Application of Ru(bpy)(3)(2+) in control and formation of gold surface nanostructure through oxidation-reduction cycling

It was studied that the nanostructure formed on a gold surface via a simple oxidation-reduction cycles (ORC) in 0.1 M KCl containing Ru(bpy)(3)(2+) with different concentrations. Atomic force microscopy (AFM) and energy-dispersed spectroscopy (EDS) were used to characterize the nanostructure formed on the gold surface. Sweep-step voltammetry and corresponding electroluminescence (ECL) response, in situ electrochemical quartz crystal microbalance (EQCM) measurement were used to monitor the ORC. procedure. It was found that the surface structure became more uniform in the presence of Ru(bpy)(3)(2+), and the surface roughness was decreasing with the increasing of Ru(bpY)(3)(2+) concentration, suggesting a simple and effective method to control the formation of nanostructure on the gold surface.

Crystal structures and elastic properties of superhard IrN2 and IrN3 from first principles

First principles calculations were performed to investigate the structural, elastic, and electronic properties of IrN2 for various space groups: cubic Fm-3m and Pa-3, hexagonal P3(2)21, tetragonal P4(2)/mnm, orthorhombic Pmmn, Pnnm, and Pnn2, and monoclinic P2(1)/c. Our calculation indicates that the P2(1)/c phase with arsenopyrite-type structure is energetically more stable than the other phases. It is semiconducting (the remaining phases are metallic) and contains diatomic N-N with the bond distance of 1.414 A. These characters are consistent with the experimental facts that IrN2 is in lower symmetry and nonmetallic. Our conclusion is also in agreement with the recent theoretical studies that the most stable phase of IrN2 is monoclinic P2(1)/c. The calculated bulk modulus of 373 GPa is also the highest among the considered space groups. It matches the recent theoretical values of 357 GPa within 4.3% and of 402 GPa within 7.8%, but smaller than the experimental value of 428 GPa by 14.7%. Chemical bonding and potential displacive phase transitions are discussed for IrN2. For IrN3, cubic skutterudite structure (Im-3) was assumed.

CE with electrochemical detection for investigation of label-free recognition of amino acid amides by guanine-rich DNA aptamers

In this work, we report a simple and effective investigation into adaptive interactions between guanine-rich DNA aptamers and amino acid amides by CE with electrochemical (EC) detection. Argininamide (Arm) and tyrosinamide (Tym) were chosen as model molecules. On a copper electrode, Arm generated a good EC signal in 60 mM NaOH at 0.7 V (vs Ag/ AgCl), while Tym. was detected well on a platinum electrode at 1. 3 V in 20 mM phosphate of pH 7.0. Based on their EC properties, the ligands themselves were used as indicators for the adaptive interactions investigated by CE-EC, making any step of labeling and/or modification of aptamers with indicators exempted. Hydrophilic ionic liquid was used as an additive in running buffer of CE to improve the sensitivity of Arm detection, whereas the additive was not used for Tym. detection due to its negative effect. Two guanine-rich DNA aptamers were used for molecular recognition of Arm and Tym. When the aptamers were incubated with ligands, they bound the model molecules with high affinity and specificity, reflected by obvious decreases in the signals of ligands but no changes in those of the control molecules. However, the ligands were hardly affected by the control ssDNAs after incubation. The results revealed the specific recognition of Arm and Tym. by the aptamers.

An effective hydrothermal route for the synthesis of multiple PDDA-protected noble-metal nanostructures

In this Article, we demonstrate an effective hydrothermal route for the synthesis of multiple PDDA-protected (PDDA = poly(diallyl dimethylammonium) chloride) noble-metal (including silver, platinum, palladium, and gold) nanostructures in the absence of any seeds and surfactants, in which PDDA, an ordinary and water-soluble polyelectrolyte, acts as both a reducing and a stabilizing agent. Under optimal experimental conditions, Ag nanocubes, Pt and Pd nanopolyhedrons, and Au nanoplates can be obtained, which were characterized by transmission electron microscopy, scanning electron microscopy, energy-dispersive spectroscopy, and X-ray diffraction. More importantly, the nanostrucfures synthesized show potential applications in surface-enhanced Raman scattering and electrocatalysis, in which Ag nanocubes and Pt nanopolyhedrons were chosen as the examples, respectively.

Self-assembly of ionic liquids-stabilized Pt nanoparticles into two-dimensional patterned nanostructures at the air-water interface

In this paper, we demonstrate the self-assembly of ionic liquids (ILs)-stabilized Pt nanoparticles into two-dimensional (2D) patterned nanostructures at the air-water interface under ambient conditions. Here, ILs are not used as solvents but as mediators by virtue of their pronounced self-organization ability in synthesis of self-assembled, highly organized hybrid Pt nanostructures. It is also found that the morphologies of the 2D patterned nanostructures are directly connected with the quantities of ILs. Due to the special structures of ILs-stabilized Pt nanoparticles, 2D patterned Pt nanostructures can be formed through the pi-pi stack interactions and hydrogen bonds. The resulting 2D patterned Pt nanostructures exhibit good electrocatalytic activity toward oxygen reduction.

Electrochemical designing of Au/Pt core shell nanoparticles as nanostructured catalyst with tunable activity for oxygen reduction

Au/Pt core shell nanoparticles (NPs) have been prepared via a layer-by-layer growth of Pt layers on An NPs using underpotential deposition (UPD) redox replacement technique. A single UPD Cu monolayer replacement with Pt(11) yielded a uniform Pt film on Au NPs, and the shell thickness can be tuned by controlling the number of UPD redox replacement cycles. Oxygen reduction reaction (ORR) in air-saturated 0.1 M H2SO4 was used to investigate the electrocatalytic behavior of the as-prepared core shell NPs. Cyclic voltammograms of ORR show that the peak potentials shift positively from 0.32 V to 0.48 V with the number of Pt layers increasing from one to five, suggesting the electrocatalytic activity increases with increasing the thickness of Pt shell. The increase in electrocatalytic activity may originate mostly from the large decrease of electronic influence of Au cores on surface Pt atoms. Rotating ring-disk electrode voltammetry and rotating disk electrode voltammetry demonstrate that ORR is mainly a four-electron reduction on the as-prepared modified electrode with 5 Pt layers and first charge transfer is the rate-determining step.

Solution-processible multi-component cyclometalated iridium phosphors for high-efficiency orange-emitting OLEDs and their potential use as white light sources

The synthesis and photophysical studies of several multifunctional phosphorescent iridium(III) cyclometalated complexes consisting of the hole-transporting carbazole and fluorene-based 2-phenylpyridine moieties are reported. All of them are isolated as thermally and morphological stable amorphous solids. Extension of the pi-conjugation through incorporation of electron- pushing carbazole units to the fluorene fragment leads to bathochromic shifts in the emission profile, increases the highest oc- cupied molecular orbital levels and improves the charge balance in the resulting complexes because of the propensity of the carbazole unit to facilitate hole transport. These iridium-based triplet emitters give a strong orange phosphorescence light at room temperature with relatively short lifetimes in the solution phase. The photo- and electroluminescence properties of these phosphorescent carbazolylfluorene-functionalized metalated complexes have been studied in terms of the coordinating position of carbazole to the fluorene unit. Organic light-emitting diodes (OLEDs) using these complexes as the solution-processed emissive layers have been fabricated which show very high efficiencies even without the need for the typical hole-transporting layer.I These orange-emitting devices can produce a maximum current efficiency of similar to 30 cd A(-1) corresponding to an external quantum efficiency of similar to 10 % ph/el (photons per electron) and a power efficiency of similar to 14 Im W-1.

Tuning the energy level and photophysical and electroluminescent properties of heavy metal complexes by controlling the ligation of the metal with the carbon of the carbazole unit

Four novel Ir-III and Pt-II complexes with cyclometalated ligands bearing a carbazole framework are prepared and characterized by elemental analysis, NMR spectroscopy, and mass spectrometry. Single-crystal X-ray diffraction studies of complexes 1, 3, and 4 reveal that the 3- or 2-position C atom of the carbazole unit coordinates to the metal center. The difference in the ligation position results in significant shifts in the emission spectra with the changes in wavelength being 84 nm for the Ir complexes and 63 nm for the Pt complexes. The electrochemical behavior and photophysical properties of the complexes are investigated, and correlate well with the results of density functional theory (DFT) calculations. Electroluminescent devices with a configuration of ITO/NPB/CBP:dopant/BCP/AlQ(3)/LiF/Al can attain very high efficiencies.

(R,R)-DPEN-modified Ru/gamma-Al2O3 - An efficient heterogeneous catalyst for enantioselective hydrogenation of acetophenone

An efficient enantioselective catalyst of 5 wt.% Ru/-gamma-Al2O3 modified with R,R-1,2-diphenylethylene-diamine ((R,R)-DPEN) for the hydrogenation of a non-activated aromatic ketone of acetophenone has been investigated, a relatively high enantiomeric excess (ee) of 60.5% was obtained at both the conversion and selectivity larger than 99%, it was about three times higher than the ee values reported up to now for acetophenone hydrogenation with the supported transition metal catalysts modified by chiral reagents. The influences of some reaction parameters such as phosphine ligand, substrate/catalyst/modifier molar ratios, base, solvent, pressure and reaction temperature have been discussed. The chiral modifier of (R,R)-DPEN was very important in controlling the enantioselectivity through adsorption competing with other substrates on the surface of active metal species. The phosphine ligand and base were also important and indispensable in the present reaction.

The real role of carbon in Pt/C catalysts for oxygen reduction reaction

A new electrocatalysis of carbon materials for oxygen reduction reaction (ORR) on Pt/C catalysts was discovered. It was found that there exist two kinds of electroactive sites on these supports of carbon materials, which can effectively electrocatalyze the reduction of peroxide intermediated from oxygen reduction on Pt, as this provides continuous driving force to move the equilibrium toward the production of peroxide from ORR.