Mo2 C-Based Ceramic Electrode with High Stability and Catalytic Activity for Hydrogen Evolution Reaction at High Current Density.

Developing robust electrodes with high catalytic performance is a key step for expanding practical HER (hydrogen evolution reaction) applications. This paper reports on novel porous Mo2 C-based ceramics with oriented finger-like holes directly used as self-supported HER electrodes. Due to the suitable MoO3 sintering additive, high-strength (55 ± 6 MPa) ceramic substrates and a highly active catalytic layer are produced in one step. The in situ reaction between MoO3 and Mo2 C enabled the introduction of O in the Mo2 C crystal lattice and the formation of Mo2 C(O)/MoO2 heterostructures. The optimal Mo2 C-based electrode displayed an overpotential of 333 and 212 mV at 70 °C under a high current intensity of 1500 mA cm-2 in 0.5 m H2 SO4 and 1.0 m KOH, respectively, which are markedly better than the performance of Pt wire electrode; furthermore, its price is three orders of magnitude lower than Pt. The chronopotentiometric curves recorded in the 50 - 1500 mA cm-2 range, confirmed its excellent long-term stability in acidic and alkaline media for more than 260 h. Density functional theory (DFT) calculations showed that the Mo2 C(O)/MoO2 heterostructures has an optimum electronic structure with appropriate *H adsorption-free energy in an acidic medium and minimum water dissociation energy barrier in an alkaline medium.

Robust Porous WC-Based Self-Supported Ceramic Electrodes for High Current Density Hydrogen Evolution Reaction.

Developing an economical, durable, and efficient electrode that performs well at high current densities and is capable of satisfying large-scale electrochemical hydrogen production is highly demanded. A self-supported electrocatalytic "Pt-like" WC porous electrode with open finger-like holes is produced through industrial processes, and a tightly bonded nitrogen-doped WC/W (WC-N/W) heterostructure is formed in situ on the WC grains. The obtained WC-N/W electrode manifests excellent durability and stability under multi-step current density in the range of 30-1000 mA cm-2 for more than 220 h in both acidic and alkaline media. Although WC is three orders of magnitude cheaper than Pt, the produced electrode demonstrates comparable hydrogen evolution reaction performance to the Pt electrode at high current density. Density functional theory calculations attribute its superior performance to the electrode structure and the modulated electronic structure at the WC-N/W interface.

Mechanism of upconversion luminescence enhancement in Yb3+/Er3+ co-doped Y2O3 through Li+ incorporation.

Li+ doping is a well-known, simple, yet efficient strategy to optimize the properties of upconverting materials. Nonetheless, the position of Li+ in the lattice and the mechanism of upconversion enhancement are still controversial, especially in Yb3+/Er3+ co-doped Y2O3. This paper presents a comprehensive investigation of the above issues (i.e. the position occupied by Li+ in the lattice and the mechanism of luminescence enhancement, in terms of decreased defects) by studying (Y0.78-XYb0.20Er0.02LiX)2O3 powders. Neutron powder diffraction was employed for the first time in the literature to show that Li+ ions are accommodated in Y sites of YO6 octahedra, confirmed also by the content of oxygen defects, which was increased with the increase of Li+ concentration. FT-IR showed that there was a small change in the amount and the type of the surface-absorbed groups with the increase in the Li+ content, thus not supporting the prevailing conclusion that the quenching groups are decreased by doping Li+. Positron annihilation lifetime (PLAS) experiments showed that the total defect concentration and the large defect clusters, which are considered as quenching centers, are decreased with increasing Li+-content, resulting in the enhancement of the emission intensity in Yb3+/Er3+ co-doped Y2O3.

Simple Fabrication of Concrete with Remarkable Self-Cleaning Ability, Robust Superhydrophobicity, Tailored Porosity, and Highly Thermal and Sound Insulation.

Self-cleaning materials have attracted immense commercial and academic interests in recent years. A major challenge is the scalable and cost-effective fabrication of three-dimensional bulk materials with remarkable self-cleaning and a desirable combination of tailored porosity, robust superhydrophobicity, excellent mechanical strength, heat insulation, and sound absorption ability. Here, self-cleaning concrete was achieved in one step through the combination of the liquid template pore formation and in situ bulk hydrophobic modification. The concrete exhibited superhydrophobicity with a high water contact angle of 166° both on the surface and inside of the sample, which qualified the sample with remarkable stain repellency and long-term stability. The water contact angle remained unchanged under continuous mechanical grinding and harsh environments, such as high temperature (450 °C in air and 650 °C in Ar) and chemical erosion. The concrete with a controllable porosity from 56.3 to 77.4% and homogeneous small pore size (∼15 µm) exhibited high compressive strength and low thermal conductivity. Furthermore, high sound absorption capacity (97%, 500 Hz) at a vibration frequency from 400 to 600 Hz was realized. With these excellent performances and characteristics and easy scalable fabrication, the concrete prepared in this work possessed a wide application prospect.

The crystal structure and luminescence properties of a novel green-yellow emitting Ca1.5Mg0.5Si1-xLixO4-δ:Ce3+ phosphor with high quantum efficiency and thermal stability.

A novel green-yellow emitting Ca1.5Mg0.5Si1-xLixO4-δ:Ce3+ phosphor with high quantum efficiency and thermal stability was discovered for applications in near ultraviolet pumped white light-emitting diodes. Its crystal structure was determined with a single-particle diagnosis approach. The Si sites in the SiO4 tetrahedra are reported for the first time to accommodate Li+ ions. This substitution, confirmed by 6Li solid-state NMR and T.O.F. neutron powder diffraction, causes a disordered occupation of Ca/Mg in the Ca3MgSi2O8 host and favors a phase transformation at ∼330 °C, which results in the formation of the novel phosphor. The produced phosphor was efficiently excited by near UV light peaking at 365 and 410 nm and produced broad green-yellow emission with peaks at 500 and 560 nm, respectively. Its quantum efficiency reached 88.4% (internal) and 55.7% (external) under excitation at 365 nm, and 80.5% (internal) and 42.7% (external) under excitation at 410 nm, while the decrease of luminescence intensity at 200 °C was small (∼26%). A WLED lamp with a high color rendering index of Ra = 92.8 was produced with the combination of a 365 nm emitting chip with blue emitting BaMgAl10O17:Eu2+, green-yellow emitting CMSL:0.01Ce, and red emitting Sr2Si5N8:Eu2+ phosphors.

Preparation of a Porous, Sintered and Reaction-Bonded Si3N4 (SRBSN) Planar Membrane for Filtration of an Oil-in-Water Emulsion with High Flux Performance.

A porous, sintered, and reaction-bonded Si3N4 (SRBSN) planar membrane was prepared by phase-inversion tape-casting, nitridation (at 1350 °C), and sintering (at 1650 °C) of silicon slurry. The membrane was comprised of uniform rod-like β-Si3N4 crystals with a large length/diameter ratio and had high porosity and bending strength. The prepared membrane features a typical asymmetric structure with a skin layer, a sponge layer, and finger-like voids and an average pore size of 0.61 μm. A high permeation flux of 367 L m−2 h−1 and an oil rejection of 88.6% were recorded in oil-in-water emulsion separation experiments. These results suggest that SRBSN membranes have excellent potential for the treatment of oily wastewater.

Synthesis of Si, N co-Doped Nano-Sized TiO2 with High Thermal Stability and Photocatalytic Activity by Mechanochemical Method.

Τhe photocatalytic activity in the range of visible light wavelengths and the thermal stability of the structure were significantly enhanced in Si, N co-doped nano-sized TiO2, and synthesized through high-energy mechanical milling of TiO2 and SiO2 powders, which was followed by calcination at 600 °C in an ammonia atmosphere. High-energy mechanical milling had a pronounced effect on the mixing and the reaction between the starting powders and greatly favored the transformation of the resultant powder mixture into an amorphous phase that contained a large number of evenly-dispersed nanocrystalline TiO2 particles as anatase seeds. The experimental results suggest that the elements were homogeneously dispersed at an atomic level in this amorphous phase. After calcination, most of the amorphous phase was crystallized, which resulted in a unique nano-sized crystalline-core/disordered-shell morphology. This novel experimental process is simple, template-free, and provides features of high reproducibility in large-scale industrial production.

Single-Phase White Light-Emitting Ca x Ba(9-x)Lu2Si6O24:Eu2+/Mn2+ Phosphors.

Single-phase white light-emitting Ca x Ba(9-x)Lu2Si6O24:Eu2+/Mn2+ codoped phosphors were successfully synthesized, and their photoluminescence properties were experimentally determined. The analysis of the experimental results suggests that the partial substitution of Ba2+ ions by smaller Ca2+ ions alters the distribution of the Eu2+ luminescence center among the three available Ba2+ sites in the host lattice, which enables the emission to be efficiently tuned from blue to blue-green-yellow region. The incorporation of Mn2+ ions resulted in a red light emission at around 618 nm, through energy transfer from Eu2+ to Mn2+ ions via dipole-dipole interactions. The incorporation of Ca2+ and Mn2+ ions also resulted in improved thermal stability. The results qualify the produced Ca x Ba(9-x)Lu2Si6O24:Eu2+/Mn2+ composition as a potential ultraviolet-convertible white light-emitting phosphor.

Role of oxygen vacancy on the photoluminescence of BaMgSiO4:Eu phosphors: experimental and theoretical analysis.

Pure BaMgSiO4:Eu(2+) phosphor, prepared by a solid state reaction method under N2 atmosphere, exhibited a strong green emission at 500 nm and a weak emission at 405 nm. Heat treatment under NH3 atmosphere causes changes in the PL intensity: the green emission at 500 nm gradually decreases and completely disappears after heat treatment for 3 h, whereas a new blue emission peak, centered at 445 nm, appears and becomes very strong. The results of the analyses with electron paramagnetic resonance (EPR), X-ray photoelectron spectroscopy (XPS), and X-ray absorption fine structure (XAFS) spectroscopy suggest that the heat treatment causes the generation of a large amount of oxygen vacancies. This resulted in the aforementioned color changes of the BaMgSiO4:Eu phosphor, which are confirmed by the results of DFT+U calculations. In particular, these calculations showed that Eu prefers to occupy Ba(3) sites, which are six coordinated to oxygen atoms. The emission at 500 nm was attributed to the 4f-5d transition energy of Eu in Ba(3) site, calculated as 2.54 eV. It was also shown that Eu 4f energy level decreases when oxygen is removed from the oxygen position adjacent to Eu, which results in a larger Eu 4f-5d transition energy and shorter wavelengths of emission peaks.