Formation mechanism of Mn x Co3-x O4 yolk-shell structures.

Formation of Mn x Co3-x O4 yolk-shell microspheres via a solvothermal reaction of hydrated cobalt and manganese nitrates in ethanol is investigated. Spinel nanocrystals of cobalt oxide or cobalt-rich ternary oxide preferentially develop in the system, while manganese-rich hydroxide form Mn(OH)2-type nanosheets. Instead of continuing to grow individually, the nanocrystallites and nanosheets aggregate into large microspheres due to their strong inter-particle interaction. When the proportion of Mn-rich nanosheets is high, therefore the overall density is low, dehydration of hydroxide nanosheets and a surface re-crystallisation lead to formation of a dense and rigid shell, which is separated from a solid or hollow core via a further Ostwald ripening process. The proposed formation mechanism of the yolk-shell structures based on electron microscopic studies would help us to develop yolk-shell structure based multifunctional materials.

Toward New Thermoelectrics: Tin Selenide/Modified Graphene Oxide Nanocomposites.

New nanocomposites have been prepared by combining tin selenide (SnSe) with graphene oxide (GO) in a simple aqueous solution process followed by ice templating (freeze casting). The resulting integration of SnSe within the GO matrix leads to modifications of electrical transport properties and the possibility of influencing the power factor (S 2σ). Moreover, these transport properties can then be further improved (S, σ increased) by functionalization of the GO surface to form modified nanocomposites (SnSe/GOmod) with enhanced power factors in comparison to unmodified nanocomposites (SnSe/GO) and "bare" SnSe itself. Functionalizing the GO by reaction with octadecyltrimethoxysilane (C21H46O3Si) and triethylamine ((CH3CH2)3N) switches SnSe from p-type to n-type conductivity with an appreciable Seebeck coefficient and high electrical conductivity (1257 S·m-1 at 539 K), yielding a 20-fold increase in the power factor compared to SnSe itself, prepared by the same route. These findings present new possibilities to design inexpensive and porous nanocomposites based on metal chalcogenides and functionalized carbon-derived matrices.

Control of Luminescence by Tuning of Crystal Symmetry and Local Structure in Mn4+ -Activated Narrow Band Fluoride Phosphors.

Mn4+ -doped fluoride phosphors have been widely used in wide-gamut backlighting devices because of their extremely narrow emission band. Solid solutions of Na2 (Six Ge1-x )F6 :Mn4+ and Na2 (Gey Ti1-y )F6 :Mn4+ were successfully synthesized to elucidate the behavior of the zero-phonon line (ZPL) in different structures. The ratio between ZPL and the highest emission intensity υ6 phonon sideband exhibits a strong relationship with luminescent decay rate. First-principles calculations are conducted to model the variation in the structural and electronic properties of the prepared solid solutions as a function of the composition. To compensate for the limitations of the Rietveld refinement, electron paramagnetic resonance and high-resolution steady-state emission spectra are used to confirm the diverse local environment for Mn4+ in the structure. Finally, the spectral luminous efficacy of radiation (LER) is used to reveal the important role of ZPL in practical applications.

Aluminate Red Phosphor in Light-Emitting Diodes: Theoretical Calculations, Charge Varieties, and High-Pressure Luminescence Analysis.

Searching for a non-rare-earth-based oxide red-emitting phosphor is crucial for phosphor-converted light-emitting diodes (LEDs). In this study, we optimized a blue and UV-light excited Sr4Al14O25:Mn phosphor exhibiting red emission peaked at ∼653 nm, which was successfully synthesized by solid-state reaction. The crystal structure, micromorphology, and luminescent properties of Sr4Al14O25:Mn phosphors were characterized by X-ray Rietveld refinement, high-resolution transmission electron microscopy, and photoluminescence spectra. The band gap and electronic structure of Sr4Al14O25 were analyzed by density functional theory calculations using the hybrid exchange-correlation functional. The crystal field environment effect of Al sites from introducing activator Mn ions was investigated with the aid of Raman 27Al nuclear magnetic resonance spectra and electron spin resonance. The pressure dependent luminescent properties and decay time of this compound were presented. The tricolor display spectrum by combining blue InGaN chips, commercial ß-SiAlON:Eu2+ green phosphor, and Sr4Al14O25:Mn red phosphor were evaluated for commercial applications: using the present Sr4Al14O25:Mn red phosphor converted LED as a backlighting source.

Metal-Organic-Framework-Derived Hybrid Carbon Nanocages as a Bifunctional Electrocatalyst for Oxygen Reduction and Evolution.

The oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are cornerstone reactions for many renewable energy technologies. Developing cheap yet durable substitutes of precious-metal catalysts, especially the bifunctional electrocatalysts with high activity for both ORR and OER reactions and their streamlined coupling process, are highly desirable to reduce the processing cost and complexity of renewable energy systems. Here, a facile strategy is reported for synthesizing double-shelled hybrid nanocages with outer shells of Co-N-doped graphitic carbon (Co-NGC) and inner shells of N-doped microporous carbon (NC) by templating against core-shell metal-organic frameworks. The double-shelled NC@Co-NGC nanocages well integrate the high activity of Co-NGC shells into the robust NC hollow framework with enhanced diffusion kinetics, exhibiting superior electrocatalytic properties to Pt and RuO2 as a bifunctional electrocatalyst for ORR and OER, and hold a promise as efficient air electrode catalysts in Zn-air batteries. First-principles calculations reveal that the high catalytic activities of Co-NGC shells are due to the synergistic electron transfer and redistribution between the Co nanoparticles, the graphitic carbon, and the doped N species. Strong yet favorable adsorption of an OOH* intermediate on the high density of uncoordinated hollow-site C atoms with respect to the Co lattice in the Co-NGC structure is a vital rate-determining step to achieve excellent bifunctional electrocatalytic activity.

Structural Ordering and Charge Variation Induced by Cation Substitution in (Sr,Ca)AlSiN3:Eu Phosphor.

Nitride phosphors are suitable for white light-emitting diode applications. In this study, the structure of phosphor has been modified through cation substitution to induce charge variation and a rearrangement of neighboring nitride clusters, and consequently enhance its luminescent behavior. Substitution of Ca(2+) by Sr(2+) cations expanded the lattice volume and the bc plane, but shortened the distance between the layers along the a axis. Lattice distortion of the framework introduced high-coordination sites in the Sr/Eu centers and adequate space, thereby facilitating charge variation of activators under reduced atmosphere, as detected through X-ray absorption near-edge structure spectroscopy. As such, the photoluminescent intensity of the phosphors increased by more than 10% and a blue shift occurred. The microstructures of the samples were also analyzed using high-resolution transmission electron microscopy. Cation substitution induced a special change in the anion environment, as indicated in the solid-state Raman spectra. Moreover, typical ordering variations in the SiN4 and AlN4 clusters are generated in the lattice. Meanwhile, neighbor sequence of (Si/Al)N4 around the divalent centers were observed through solid-state nuclear magnetic resonance spectroscopy. The modified ordering distribution resulted in a rigid structure and improved the thermal quenching behavior. Thermal stability has been enhanced by 10% at 473 K when x = 0.9 in SrxCa0.993-xAlSiN3:Eu(2+)0.007 compared with that at x = 0. This study promotes the research of neighbor sequence for selective tetrahedral sites such as Li, Mg, Al, and Si coordinated by N atoms in contact with cation sites.

The role of surface hydrolysis of ferricyanide anions in crystal growth of snowflake-shaped α-Fe2O3.

Selective adsorption and surface hydrolysis of [Fe(CN)6](3-) anions on α-Fe2O3 crystals was found to be a crucial process in the formation of a snowflake-like morphology, and the established mechanism is complementary to the classical theories of crystal growth.

Domination of second-sphere shrinkage effect to improve photoluminescence of red nitride phosphors.

Red Ca0.99Al(1-4δ/3-x)Si(1+δ+x)N(3-x)C(x):Eu(2+)0.01 (δ = 0.345; x = 0-0.2) nitride phosphors exhibit a blue-shifted emission with increased eye sensitivity function and excellent thermal stability. The variations in the photoluminescence in the Ca0.99Al(1-4δ/3-x)Si(1+δ+x)N(3-x)C(x):Eu(2+)0.01 (δ = 0.345; x = 0-0.2) system are thoroughly investigated. The enhanced emission energy and the improved thermal stability with increasing x are dominated by the second-sphere shrinkage effect via the substitution of small Si(4+) for large Al(3+) with simultaneous charge compensation. Related proofs of the second-sphere shrinkage effect control for photoluminescence are confirmed via high-resolution neutron powder diffraction, EXAFS, and (29)Si solid-state NMR techniques.