Green synthesis, structure feature and energy transfer of yellow-emitting (Y,Gd)2 O2 SO4 :Dy phosphors.

A green chemical precipitation route was used to yield a hydrated basic sulfate precursor upon calcination at 1000°C into a series of (Y,Gd)2 O2 SO4 :Dy particles. The phosphors exhibited characteristic Dy3+ emissions from 4 F9/2 →6 HJ (J = 15/2, 13/2, 11/2) transitions under ultraviolet light excitation; the quenching concentration of Dy3+ was determined to be 2.5 at.%. Substitution of Gd3+ for Y3+ led to an additional strong sharp band at ~277 nm (8 S7/2 →6 IJ transition of Gd3+ ) in the photoluminescence excitation spectra, upon which the (Gd0.975 Dy0.025 )2 O2 SO4 phosphor achieved a ~2.8-fold higher photoluminescence intensity via an effective energy transfer from Gd3+ to Dy3+ compared with the 354 nm excitation of Dy3+ . Both the photoluminescence and photoluminescence excitation intensities of (Y,Gd)2 O2 SO4 :Dy phosphors increased with rising Gd3+ concentration and calcination temperature in the range 750-1000°C. A higher Gd3+ concentration slightly prolonged the effective fluorescence lifetime.

Amorphous Alloy Architectures in Pore Walls: Mesoporous Amorphous NiCoB Alloy Spheres with Controlled Compositions via a Chemical Reduction.

Amorphous bimetallic borides are an emerging class of catalytic nanomaterial that has demonstrated excellent catalytic performance due to its glass-like structure, abundant unsaturated active sites, and synergistic electronic effects. However, the creation of mesoporous Earth-abundant bimetallic metal borides with tunable metal proportion remains a challenge. Herein, we develop a sophisticated and controllable dual-reducing agent strategy to synthesize the mesoporous nickel-cobalt boron (NiCoB) amorphous alloy spheres (AASs) with adjustable compositions by using a soft template-directed assembly approach. The selective use of tetrabutylphosphonium bromide (Bu4PBr) is beneficial to generate well-defined mesopores because it both moderates the reduction rate by decreasing the reducibility of M2+ species and prevents the generation of soap bubbles. Our meso-Ni10.0Co74.5B15.5 AASs generate the highest catalytic performance for the hydrolytic dehydrogenation of ammonia borane (AB). Its high performance is attributed to the combination of optimal synergistic effects between Ni, Co, and B as well as the high surface area and the good mass transport efficiency due to the open mesopores. This work describes a systematic approach for the design and synthesis of mesoporous bimetallic borides as efficient catalysts.

A mesoporous non-precious metal boride system: synthesis of mesoporous cobalt boride by strictly controlled chemical reduction.

Generating high surface area mesoporous transition metal boride is interesting because the incorporation of boron atoms generates lattice distortions that lead to the formation of amorphous metal boride with unique properties in catalysis. Here we report the first synthesis of mesoporous cobalt boron amorphous alloy colloidal particles using a soft template-directed assembly approach. Dual reducing agents are used to precisely control the chemical reduction process of mesoporous cobalt boron nanospheres. The Earth-abundance of cobalt boride combined with the high surface area and mesoporous nanoarchitecture enables solar-energy efficient photothermal conversion of CO2 into CO compared to non-porous cobalt boron alloys and commercial cobalt catalysts.

EDTA-assisted phase conversion synthesis of (Gd0.95RE0.05)PO4 nanowires (RE = Eu, Tb) and investigation of photoluminescence.

Hexagonal (Gd0.95RE0.05)PO4·nH2O nanowires ~300 nm in length and ~10 nm in diameter have been converted from (Gd0.95RE0.05)2(OH)5NO3·nH2O nanosheets (RE = Eu, Tb) in the presence of monoammonium phosphate (NH4H2PO4) and ethylene diamine tetraacetic acid (EDTA). They were characterized by X-ray diffraction, thermogravimetry, electron microscopy, and Fourier transform infrared and photoluminescence spectroscopies. It is shown that EDTA played an essential role in the morphology development of the nanowires. The hydrothermal products obtained up to 180 °C are of a pure hexagonal phase, while monoclinic phosphate evolved as an impurity at 200 °C. The nanowires undergo hexagonal→monoclinic phase transformation upon calcination at ≥600 °C to yield a pure monoclinic phase at ~900 °C. The effects of calcination on morphology, excitation/emission, and fluorescence decay kinetics were investigated in detail with (Gd0.95Eu0.05)PO4 as example. The abnormally strong 5D0→7F4 electric dipole Eu3+ emission in the hexagonal phosphates was ascribed to site distortion. The process of energy migration was also discussed for the optically active Gd3+ and Eu3+/Tb3+ ions.

Prevention of thermal- and moisture-induced degradation of the photoluminescence properties of the Sr2Si5N8:Eu(2+) red phosphor by thermal post-treatment in N2-H2.

A red phosphor of Sr2Si5N8:Eu(2+) powder was synthesized by a solid state reaction. The synthesized phosphor was thermally post-treated in an inert and reductive N2-H2 mixed-gas atmosphere at 300-1200 °C. The main phase of the resultant phosphor was identified as Sr2Si5N8. A passivation layer of ∼0.2 µm thickness was formed around the phosphor surface via thermal treatment. Moreover, two different luminescence centers of Eu(SrI) and Eu(SrII) in the synthesized Sr2Si5N8:Eu(2+) phosphor were proposed to be responsible for 620 nm and 670 nm emissions, respectively. More interestingly, thermal- and moisture-induced degradation of PL intensity was effectively reduced by the formation of a passivation layer around the phosphor surface, that is, the relative PL intensity recovered 99.8% of the initial intensity even after encountering thermal degradation; both moisture-induced degraded external and internal QEs were merely 1% of the initial QEs. The formed surface layer was concluded to primarily prevent the Eu(2+) activator from being oxidized, based on the systemic analysis of the mechanisms of thermal- and moisture-induced degradation.

Improved galvanic replacement growth of Ag microstructures on Cu micro-grid for enhanced SERS detection of organic molecules.

Galvanic growth of Ag nano/micro-structures on Cu micro-grid was systematically studied for surface-enhanced Raman scattering (SERS) applications. Detailed characterizations via FE-SEM and HR-TEM showed that processing parameters, (reaction time, Ag(+) concentration, and PVP addition) all substantially affect thermodynamics/kinetics of the replacement reaction to yield substrates of significantly different microstructures/homogeneities and thus varied SERS performances (sensitivity, enhancement factor, and reproducibility) of the Ag substrates in the detection of R6G analyte. PVP as an additive was shown to notably alter nucleation/growth behaviors of the Ag crystals and promote the deposition of dense and uniform Ag films of nearly monodisperse polyhedrons/nanoplates through suppressing dendrites crystallization. Under optimized synthesis (50mM of Ag(+), 30s of reaction, and 700 wt.% of PVP), Ag substrates exhibiting a high Raman signal enhancement factor of ~1.1 × 10(6) and a low relative standard deviation of ~0.13 in the repeated detection of 10 µM R6G were obtained. The facile deposition and excellent performance reported in this work may allow the Ag microstructures to find wider SERS applications. Moreover, growth mechanisms of the different Ag nano/micro-structures were discussed based on extensive FE-SEM and HR-TEM analysis.

Synthesis of Highly Photocatalytic TiO2 Microflowers Based on Solvothermal Approach Using N,N-Dimethylformamide.

Crystallized anatase TiO2 microflowers with high surface area are synthesized by a simple template-free solvothermal method using N,N-dimethylformamide (DMF). Titanium sources undergo well-organized assembly in DMF to form flower-shaped TiO2 particles. After the calcination, the anatase frameworks are highly crystallized, and the surface area is increased up to 256 m2 x g(-1). The calcined TiO2 microflowers show superior photocatalytic performance over the commercially available TiO2 product (P25) in the degradation of methylene blue.

45S5 Bioglass(®)-MWCNT composite: processing and bioactivity.

Multi-walled carbon nanotube (MWCNT)-Bioglass (BG) matrix composite was fabricated using a facile and scalable aqueous colloidal processing method without using any surfactants followed by spark plasma sintering (SPS) consolidation. The individual MWCNTs were initially uniformly dispersed in water and then entirely immobilized on the BG particles during the colloidal processing, avoiding their common re-agglomeration during the water-removal and drying step, which guaranteed their uniform dispersion within the dense BG matrix after the consolidation process. SPS was used as a fast sintering technique to minimise any damage to the MWCNT structure during the high-temperature consolidation process. The electrical conductivity of BG increased by 8 orders of magnitude with the addition of 6.35 wt% of MWCNTs compared to pure BG. Short-duration tests were used in the present study as a preliminary evaluation to understand the effect of incorporating MWCNTs on osteoblast-like cells. The analysed cell proliferation, viability and phenotype expression of MG-63 cells showed inhibition on 45S5 Bioglass(®)-MWCNT composite surfaces.

Facile and green production of aqueous graphene dispersions for biomedical applications.

We proposed a facile, low cost, and green approach to produce stable aqueous graphene dispersions from graphite by sonication in aqueous bovine serum albumin (BSA) solution for biomedical applications. The production of high-quality graphene was confirmed using microscopy images, Raman spectroscopy, UV-vis spectroscopy, and XPS. In addition, ab initio calculations revealed molecular interactions between graphene and BSA. The processability of aqueous graphene dispersions was demonstrated by fabricating conductive and mechanically robust hydrogel-graphene materials.

Recent progress in advanced optical materials based on gadolinium aluminate garnet (Gd3Al5O12).

This review article summarizes the recent achievements in stabilization of the metastable lattice of gadolinium aluminate garnet (Gd3Al5O12, GAG) and the related developments of advanced optical materials, including down-conversion phosphors, up-conversion phosphors, transparent ceramics, and single crystals. Whenever possible, the materials are compared with their better known YAG and LuAG counterparts to demonstrate the merits of the GAG host. It is shown that novel emission features and significantly improved luminescence can be attained for a number of phosphor systems with the more covalent GAG lattice and the efficient energy transfer from Gd3+ to the activator. Ce3+ doped GAG-based single crystals and transparent ceramics are also shown to simultaneously possess the advantages of high theoretical density, fast scintillation decay, and high light yields, and hold great potential as scintillators for a wide range of applications. The unresolved issues are also pointed out.

Trends in electronic structures and structural properties of MAX phases: a first-principles study on M(2)AlC (M = Sc, Ti, Cr, Zr, Nb, Mo, Hf, or Ta), M(2)AlN, and hypothetical M(2)AlB phases.

MAX phases are a large family of layered ceramics with many potential structural applications. A set of first-principles calculations was performed for M(2)AlC and M(2)AlN (M = Sc, Ti, Cr, Zr, Nb, Mo, Hf, or Ta) MAX phases as well as for hypothetical M(2)AlB to investigate trends in their electronic structures, formation energies, and various mechanical properties. Analysis of the calculated data is used to extend the idea that the elastic properties of MAX phases can be controlled according to the valence electron concentration. The valence electron concentrationcan be tuned through the various combinations of transition metal and nonmetal elements.

Electric double-layer capacitors based on highly graphitized nanoporous carbons derived from ZIF-67.

Nanoporous carbons (NPCs) have large specific surface areas, good electrical and thermal conductivity, and both chemical and mechanical stability, which facilitate their use in energy storage device applications. In the present study, highly graphitized NPCs are synthesized by one-step direct carbonization of cobalt-containing zeolitic imidazolate framework-67 (ZIF-67). After chemical etching, the deposited Co content can be completely removed to prepare pure NPCs with high specific surface area, large pore volume, and intrinsic electrical conductivity (high content of sp(2) -bonded carbons). A detailed electrochemical study is performed using cyclic voltammetry and galvanostatic charge-discharge measurements. Our NPC is very promising for efficient electrodes for high-performance supercapacitor applications. A maximum specific capacitance of 238 F g(-1) is observed at a scan rate of 20 mV s(-1) . This value is very high compared to previous works on carbon-based electric double layer capacitors.

In situ TEM observation of a microcrucible mechanism of nanowire growth.

The growth of metal oxide nanowires can proceed via a number of mechanisms such as screw dislocation, vapor-liquid-solid process, or seeded growth. Transmission electron microscopy (TEM) can resolve nanowires but invariably lacks the facility for direct observation of how nanowires form. We used a transmission electron microscope equipped with an in situ heating stage to follow the growth of quaternary metal oxide nanowires. Video-rate imaging revealed barium carbonate nanoparticles diffusing through a porous matrix containing copper and yttrium oxides to subsequently act as catalytic sites for the outgrowth of Y2BaCuO5 nanowires on reaching the surface. The results suggest that sites on the rough surface of the porous matrix act as microcrucibles and thus provide insights into the mechanisms that drive metal oxide nanowire growth at high temperatures.

Reductant-free colloidal synthesis of near-IR emitting germanium nanocrystals: role of primary amine.

High temperature colloidal synthesis without using hazardous reducing agent is demonstrated here to develop a straight forward pathway for synthesizing near-IR (NIR) light emitting germanium nanocrystals (Ge NCs). The NCs were prepared by heating a mixture of germanium (II) iodide and organoamine. This article presents an important role of the primary amine which serves as a reducing agent as well as an inhibitor against oxidation by comparing with the tertiary amine. Interestingly, the difference in chemical reactivity between each amine causes the difference in major structural phase of the products. An efficient route to produce NIR light emitting Ge NCs is demonstrated.

Controlled crystallization of cyano-bridged Cu-Pt coordination polymers with two-dimensional morphology.

Two-dimensional (2D) coordination polymers (CPs) have a highly accessible surface area that permits guest molecules to effectively access the micropores in the CPs. Here we report a bottom-up synthesis of 2D cyano-bridged Cu-Pt CP nanoflakes using trisodium citrate as a chelating agent, which controls the nucleation rate and the crystal growth. The lateral sizes of the CP nanoflakes are controlled by changing the amount of trisodium citrate used. We strongly believe that our method will be useful for the preparation of other types of 2D CP nanoflakes. The 2D CPs have many active sites for catalytic and electrochemical reactions, and furthermore the assembled CPs can be used as membrane filters.

Metal-ceramic/ceramic nanostructured layered composites for solid oxide fuel cells by spark plasma sintering.

In this work, bi-layered Fe-Ni-Co-YSZ/YSZ nanostructured composites for solid oxide fuel cells were obtained using the spark plasma sintering (SPS) technique. The microstructures of the anode and electrolyte were controlled by optimization of SPS consolidation parameters. The resulting bilayers have a full dense YSZ electrolyte and porous Fe-Ni-Co/YSZ anode as well as crack-free and well-bonded anode/electrolyte interface. On the other hand, SPS under non-optimized processing parameters cannot yield the desired results. The high resistance to thermal stresses of the fabricated half-cells was achieved with Fe-Ni-Co/YSZ anode. The developed anode showed higher thermal compatibility with YSZ electrolyte than usual Ni/YSZ cermet. Thus, with the successful combination of SPS parameters and anode material, we have obtained bi-layers for SOFCs with required microstructure and thermal compatibility.

Hybrid hydrogels containing vertically aligned carbon nanotubes with anisotropic electrical conductivity for muscle myofiber fabrication.

Biological scaffolds with tunable electrical and mechanical properties are of great interest in many different fields, such as regenerative medicine, biorobotics, and biosensing. In this study, dielectrophoresis (DEP) was used to vertically align carbon nanotubes (CNTs) within methacrylated gelatin (GelMA) hydrogels in a robust, simple, and rapid manner. GelMA-aligned CNT hydrogels showed anisotropic electrical conductivity and superior mechanical properties compared with pristine GelMA hydrogels and GelMA hydrogels containing randomly distributed CNTs. Skeletal muscle cells grown on vertically aligned CNTs in GelMA hydrogels yielded a higher number of functional myofibers than cells that were cultured on hydrogels with randomly distributed CNTs and horizontally aligned CNTs, as confirmed by the expression of myogenic genes and proteins. In addition, the myogenic gene and protein expression increased more profoundly after applying electrical stimulation along the direction of the aligned CNTs due to the anisotropic conductivity of the hybrid GelMA-vertically aligned CNT hydrogels. We believe that platform could attract great attention in other biomedical applications, such as biosensing, bioelectronics, and creating functional biomedical devices.

Two-dimensional molybdenum carbides: potential thermoelectric materials of the MXene family.

A newly synthesized family of two-dimensional transition metal carbides and nitrides, so-called MXenes, exhibit metallic or semiconducting properties upon appropriate surface functionalization. Owing to their intrinsic ceramic nature, MXenes may be suitable for energy conversion applications at high temperature. Using the Boltzmann theory and first-principles electronic structure calculations, we explore the thermoelectric properties of monolayer and multilayer M2C (M = Sc, Ti, V, Zr, Nb, Mo, Hf, and Ta) and M2N (M = Ti, Zr, and Hf) MXenes functionalized with F, OH, and O groups. From our calculations, it turns out that monolayer and multilayer nanosheets of Mo2C acquire superior power factors to other MXenes upon any type of functionalization. We therefore propose the functionalized Mo2C nanosheets as potential thermoelectric materials of the MXene family. The exceptional thermoelectric properties of the functionalized Mo2C nanosheets are attributed to the peculiar t2g band shapes, which are a combination of flat and dispersive portions. These types of band shapes allow Mo2C to gain a large Seebeck coefficient and simultaneously a good electrical conductivity at low carrier concentrations.

Direct synthesis of MOF-derived nanoporous carbon with magnetic Co nanoparticles toward efficient water treatment.

Nanoporous carbon particles with magnetic Co nanoparticles (Co/NPC particles) are synthesized by one-step carbonization of zeolitic imidazolate framework-67 (ZIF-67) crystals. After the carbonization, the original ZIF-67 shapes are preserved well. Fine magnetic Co nanoparticles are well dispersed in the nanoporous carbon matrix, with the result that the Co/NPC particles show a strong magnetic response. The obtained nanoporous carbons show a high surface area and well-developed graphitized wall, thereby realizing fast molecular diffusion of methylene blue (MB) molecules with excellent adsorption performance. The Co/NPC possesses an impressive saturation capacity for MB dye compared with the commercial activated carbon. Also, the dispersed magnetic Co nanoparticles facilitate easy magnetic separation.

Controlled photocatalytic growth of Ag nanocrystals on brookite and rutile and their SERS performance.

Ag nanocrystals (NCs) were photocatalytically grown on the surfaces of brookite and rutile nanocrystals, respectively, and their surface-enhanced Raman scattering (SERS) performance was evaluated. The resultant Ag NCs exhibit different morphologies owing to the different photocatalytic capabilities of the two types of TiO2 under otherwise identical synthetic conditions. The effects of AgNO3 concentration, UV irradiation time, and UV light power on the morphology evolution and growth kinetics of the Ag NCs were systematically investigated. Moreover, PVP was found to serve as both a reductant and a capping agent in the photocatalytic reaction systems, and its presence allows morphological control of the Ag NCs. A proper amount of PVP was confirmed to favor Ag nanoplates of larger sizes and to produce SERS substrates of substantially better performance.