Interfacial engineering of POM-stabilized Ni quantum dots on porous titanium mesh for high-rate and stable alkaline hydrogen production.

The development of low-cost, high-efficiency, and stable electrocatalysts for the alkaline hydrogen evolution reaction (HER) is a key challenge because the alkaline HER kinetics is slowed by an additional water dissociation step. Herein, we report an interfacial engineering strategy for polyoxometalate (POM)-stabilized nickel (Ni) quantum dots decorated on the surface of porous titanium mesh (POMs-Ni@PTM) for high-rate and stable alkaline hydrogen production. Benefiting from the strong interfacial interactions among POMs, Ni atoms, and PTM substrates, as well as unique POM-Ni quantum dot structures, the optimized POMs-Ni@PTM electrocatalyst exhibits a remarkable alkaline HER performance with an overpotential (η10) of 30.1 mV to reach a current density of 10 mA cm-2, which is much better than those of bare Ni decorated porous titanium mesh (Ni@PTM) (η10 = 171.1 mV) and POM decorated porous titanium mesh (POMs@PTM) electrocatalysts (η10 = 493.6 mV), comparable to that of the commercial 20 wt% platinum/carbon (20% Pt/C) electrocatalyst (η10 = 20 mV). Moreover, the optimized POMs-Ni@PTM electrocatalyst demonstrates excellent stability under continuous alkaline water-splitting at a current density of ∼100 mA cm-2 for 100 h, demonstrating great potential for its practical application.

Interfacial Thermal Conductance between Cu and Diamond with Interconnected W-W2C Interlayer.

Manipulating the interfacial structure is vital to enhancing the interfacial thermal conductance (G) in Cu/diamond composites for promising thermal management applications. An interconnected interlayer is frequently observed in Cu/diamond composites; however, the G between Cu and diamond with an interconnected interlayer has not been addressed so far and thus is attracting extensive attention in the field. In this study, we designed three kinds of interlayers between a Cu film and a diamond substrate by magnetron sputtering coupled with heat treatment, including a W interlayer, an interconnected W-W2C interlayer, and a W2C interlayer, to comparatively elucidate the relationship between the interfacial structure and the interfacial thermal conductance. For the first time, we experimentally measured the G between Cu and diamond with an interconnected interlayer by a time-domain thermoreflectance technique. The Cu/W-W2C/diamond structure exhibits an intermediate G value of 25.8 MW/m2 K, higher than the 19.9 MW/m2 K value for the Cu/W2C/diamond structure and lower than the 29.4 MW/m2 K value for the Cu/W/diamond structure. The molecular dynamics simulations show that the G of the individual W2C/diamond interface is much higher than those of the individual Cu/diamond and W/diamond interfaces and W2C could reduce the vibrational mismatch between Cu and diamond; however, the G of the Cu/W2C/diamond structure is reduced by the lower thermal conductivity of W2C. This study provides insights into the relationship between the interconnected interfacial structure and the G between Cu and diamond and offers guidance for interface design to improve the thermal conductivity in Cu/diamond composites.

Steered polymorphic nanodomains in TiO2 to boost visible-light photocatalytic oxidation.

A breakthrough in enhancing visible-light photocatalysis of wide-bandgap semiconductors such as prototypical titania (TiO2) via cocatalyst decoration is still challenged by insufficient heterojunctions and inevitable interfacial transport issues. Herein, we report a novel TiO2-based composite material composed of in situ generated polymorphic nanodomains including carbon nitride (C3N4) and (001)/(101)-faceted anatase nanocrystals. The introduction of ultrafine C3N4 results in the generation of many oxygen vacancies in the TiO2 lattice, and simultaneously induces the exposure and growth of anatase TiO2(001) facets with high surface energy. The photocatalytic performance of C3N4-induced TiO2 for degradation of 2,4-dichlorophenol under visible-light irradiation was tested, its apparent rate being up to 1.49 × 10-2 min-1, almost 3.8 times as high as that for the pure TiO2 nanofibers. More significantly, even under low operation temperature and after a long-term photocatalytic process, the composite still exhibits exceptional degradation efficiency and stability. The normalized degradation efficiency and effective lifespan of the composite photocatalyst are far superior to other reported modified photocatalysts.

Precise control of versatile microstructure and properties of graphene aerogel via freezing manipulation.

A deep understanding of the shaping technique is urgently required to precisely tailor the pore structure of a graphene aerogel (GA) in order to fit versatile application backgrounds. In the present study, the microstructure and properties of GA were regulated by freeze-casting using an ice crystal template frozen from -10 °C to -196 °C. The phase field simulation method was applied to probe the microstructural evolution of the graphene-H2O system during freezing. Both the experimental and simulation results suggested that the undercooling degree was fundamental to the nucleation and growth of ice crystals and dominated the derived morphology of GA. The pore size of GA was largely regulated from 240 to 6 µm via decreasing the freezing temperature from -10 °C to -196 °C but with a constant density of 8.3 mg cm-3. Rapid freeze casting endowed GA with a refined pore structure and therefore better thermal, electrical, and compressive properties, whereas the GA frozen slowly had superior absorption properties owing to the continuous and tube-like graphene lamellae. The GA frozen at -196 °C exhibited the highest Young's modulus of 327 kPa with similar densities to those reported in the literature. These findings demonstrate the diverse potential applications of GA with regulated pore morphologies and also contribute to cryogenic-induced phase separation methods.

InGaN light emitting diodes with a nanopipe layer formed from the GaN epitaxial layer.

A Si-heavy doped GaN:Si epitaxial layer is transformed into a directional nanopipe GaN layer through a laser-scribing process and a selectively electrochemical (EC) etching process. InGaN light-emitting diodes (LEDs) with an EC-treated nanopipe GaN layer have a high light extraction efficiency. The direction of the nanopipe structure was directed perpendicular to the laser scribing line and was guided by an external bias electric field. An InGaN LED structure with an embedded nanopipe GaN layer can enhance external quantum efficiency through a one-step epitaxial growth process and a selective EC etching process. A birefringence optical property and a low effective refractive index were observed in the directional-nanopipe GaN layer.

InGaN Light-Emitting Diodes with an Embedded Nanoporous GaN Distributed Bragg Reflectors.

InGaN light emitting diodes (LED) structure with an embedded 1/4λ-stack nanoporous-GaN/undoped-GaN distributed Bragg reflectors (DBR) structure have been demonstrated. Si-heavily doped GaN epitaxial layers (n(+)-GaN) in the 12-period n(+)-GaN/u-GaN stack structure are transformed into low refractive index nanoporous GaN structure through the doping-selective electrochemical wet etching process. The central wavelength of the nanoporous DBR structure was located at 442.3 nm with a 57 nm linewidth and a 97.1% peak reflectivity. The effective cavity length (6.0λ), the effective penetration depth (278 nm) in the nanoporous DBR structure, and InGaN active layer matching to Fabry-Pérot mode order 12 were observed in the far-field photoluminescence radiative spectra. High electroluminescence emission intensity and line-width narrowing effect were measured in the DBR-LED compared with the non-treated LED structure. Non-linear emission intensity and line-width reducing effect, from 11.8 nm to 0.73 nm, were observed by increasing the laser excited power. Resonant cavity effect was observed in the InGaN LED with bottom nanoporous-DBR and top GaN/air interface.

InGaN-based light-emitting diodes with an embedded conical air-voids structure.

The conical air-void structure of an InGaN light-emitting diode (LEDs) was formed at the GaN/sapphire interface to increase the light extraction efficiency. The fabrication process of the conical air-void structure consisted of a dry process and a crystallographic wet etching process on an undoped GaN layer, followed by a re-growth process for the InGaN LED structure. A higher light output power (1.54 times) and a small divergent angle (120°) were observed, at a 20 mA operation current, on the treated LED structure when compared to a standard LED without the conical air-void structure. In this electroluminescence spectrum, the emission intensity and the peak wavelength varied periodically by corresponding to the conical air-void patterns that were measured through a 100 nm-optical-aperture fiber probe. The conical air-void structure reduced the compressed strain at the GaN/sapphire interface by inducing the wavelength blueshift phenomenon and the higher internal quantum efficiency of the photoluminescence spectra for the treated LED structure.