Twinning Engineering of Platinum/Iridium Nanonets as Turing-Type Catalysts for Efficient Water Splitting.

The twin boundary, a common lattice plane of mirror-symmetric crystals, may have high reactivity due to special atomic coordination. However, twinning platinum and iridium nanocatalysts are grand challenges due to the high stacking fault energies that are nearly 1 order of magnitude larger than those of easy-twinning gold and silver. Here, we demonstrate that Turing structuring, realized by selective etching of superthin metal film, provides 14.3 and 18.9 times increases in twin-boundary densities for platinum and iridium nanonets, comparable to the highly twinned silver nanocatalysts. The Turing configurations with abundant low-coordination atoms contribute to the formation of nanotwins and create a large active surface area. Theoretical calculations reveal that the specific atom arrangement on the twin boundary changes the electronic structure and reduces the energy barrier of water dissociation. The optimal Turing-type platinum nanonets demonstrated excellent hydrogen-evolution-reaction performance with a 25.6 mV overpotential at 10.0 mA·cm-2 and a 14.8-fold increase in mass activity. And the bifunctional Turing iridium catalysts integrated in the water electrolyzer had a mass activity 23.0 times that of commercial iridium catalysts. This work opens a new avenue for nanocrystal twinning as a facile paradigm for designing high-performance nanocatalysts.

Turing structuring with multiple nanotwins to engineer efficient and stable catalysts for hydrogen evolution reaction.

Low-dimensional nanocrystals with controllable defects or strain modifications are newly emerging active electrocatalysts for hydrogen-energy conversion and utilization; however, a crucial challenge remains in insufficient stability due to spontaneous structural degradation and strain relaxation. Here we report a Turing structuring strategy to activate and stabilize superthin metal nanosheets by incorporating high-density nanotwins. Turing configuration, realized by constrained orientation attachment of nanograins, yields intrinsically stable nanotwin network and straining effects, which synergistically reduce the energy barrier of water dissociation and optimize the hydrogen adsorption free energy for hydrogen evolution reaction. Turing PtNiNb nanocatalyst achieves 23.5 and 3.1 times increase in mass activity and stability index, respectively, compared against commercial 20% Pt/C. The Turing PtNiNb-based anion-exchange-membrane water electrolyser with a low Pt mass loading of 0.05 mg cm-2 demonstrates at least 500 h stability at 1000 mA cm-2, disclosing the stable catalysis. Besides, this new paradigm can be extended to Ir/Pd/Ag-based nanocatalysts, illustrating the universality of Turing-type catalysts.

Micro/nano hierarchical structured titanium treated by NH4OH/H2O2 for enhancing cell response.

In this paper, two kinds of titanium surfaces with novel micro/nano hierarchical structures, namely Etched (E) surface and Sandblast and etched (SE) surface, were successfully fabricated by NH4OH and H2O2 mixture. And their cellular responses of MG63 were investigated compared with Sandblast and acid-etching (SLA) surface. Scanning electron microscope (SEM), Surface profiler, X-ray photoelectron spectroscopy (XPS), and Contact angle instrument were employed to assess the surface morphologies, roughness, chemistry and wettability respectively. Hierarchical structures with micro holes of 10-30 µm in diameter and nano pits of tens of nanometers in diameter formed on both E and SE surfaces. The size of micro holes is very close to osteoblast cell, which makes them wonderful beds for osteoblast. Moreover, these two kinds of surfaces possess similar roughness and superior hydrophilicity to SLA. Reactive oxygen species were detected on E and SE surface, and thus considerable antimicrobial performance and well fixation can be speculated on them. The cell experiments also demonstrated a boost in cell attachment, and that proliferation and osteogenic differentiation were achieved on them, especially on SE surface. The results indicate that the treatment of pure titanium with H2O2/NH4OH is an effective technique to improve the initial stability of implants and enhance the osseointegration, which may be a promising surface treatment to titanium implant.

Cell responses to titanium treated by a sandblast-free method for implant applications.

Sandblast and acid-etching (SLA) is the most prevalent treatment to titanium implants, while residual sand particles are inevitably introduced on SLA titanium surfaces. NH4OH and H2O2 mixture was used to etch titanium plates (E) and titanium bars (EB), aiming at substituting sandblast procedure. To study the effects of different scale rough structures on cell response of Human osteoblast-like cells (MG63), traditional H2SO4 and HCl mixture was also used to further etch the titanium plates above (DE). Holes of 10-20µm were obtained on E and DE surfaces, which are very close to the size of osteoblasts. Surfaces with micro/nano and micro/submicro hierarchical structures were obtained on the treated titanium. As-prepared E, DE and EB surfaces are hydrophilic, while only EB stayed hydrophilic after 5days' exposure to air. MG63 cultured on E and EB surfaces showed higher proliferation rate and attachment area than on DE and P surfaces. E and DE showed higher alkaline phosphatases (ALP) activity after 7 and 14days of osteoinduction, while EB showed the highest osteopontin (OPN) and bone sialoprotein (BSP) production after 21days of osteoinduction. These results indicate that E and EB surfaces boost the proliferation and osteogenic differentiation of MG63 without introducing sand particles. This is a promising treatment to titanium implant.

Improving the long-term stability of Ti6Al4V abutment screw by coating micro/nano-crystalline diamond films.

Abutment screw loosening is the most common complication of implanting teeth. Aimed at improving the long-term stability of them, well-adherent and homogeneous micro-crystalline diamond (MCD) and nano-crystalline diamond (NCD) were deposited on DIO(®) (Dong Seo, Korea) abutment screws using a hot filament chemical vapor deposition (HFCVD) system. Compared with bare DIO(®) screws, diamond coated ones showed higher post reverse toque values than the bare ones (p<0.05) after cyclic loading one million times under 100N, and no obvious flaking happened after loading test. Diamond coated disks showed lower friction coefficients of 0.15 and 0.18 in artificial saliva when countered with ZrO2 than that of bare Ti6Al4V disks of 0.40. Though higher cell apoptosis rate was observed on film coated disks, but no significant difference between MCD group and NCD group. And the cytotoxicity of diamond films was acceptable for the fact that the cell viability of them was still higher than 70% after cultured for 72h. It can be inferred that coating diamond films might be a promising modification method for Ti6Al4V abutment screws.

Heterotrophic respiration does not acclimate to continuous warming in a subtropical forest.

As heterotrophic respiration (R(H)) has great potential to increase atmospheric CO2 concentrations, it is important to understand warming effects on R(H) for a better prediction of carbon-climate feedbacks. However, it remains unclear how R(H) responds to warming in subtropical forests. Here, we carried out trenching alone and trenching with warming treatments to test the climate warming effect on R(H) in a subtropical forest in southwestern China. During the measurement period, warming increased annual soil temperature by 2.1 °C, and increased annual mean R(H) by 22.9%. Warming effect on soil temperature (WE(T)) showed very similar pattern with warming effect on R(H) (WE(RH)), decreasing yearly. Regression analyses suggest that WE(RH) was controlled by WE(T) and also regulated by the soil water content. These results showed that the decrease of WE(RH) was not caused by acclimation to the warmer temperature, but was instead due to decrease of WE(T). We therefore suggest that global warming will accelerate soil carbon efflux to the atmosphere, regulated by the change in soil water content in subtropical forests.

Investigation of temperature and aridity at different elevations of Mt. Ailao, SW China.

Our current understanding is that plant species distribution in the subtropical mountain forests of Southwest China is controlled mainly by inadequate warmth. Due to abundant annual precipitation, aridity has been less considered in this context, yet rainfall here is highly seasonal, and the magnitude of drought severity at different elevations has not been examined due to limited access to higher elevations in this area.In this study, short-term micrometeorological variables were measured at 2,480 m and 2,680 m, where different forest types occur. Drought stress was evaluated by combining measurements of water evaporation demand (E p) and soil volumetric water content (VWC). The results showed that: (1) mean temperature decreased 1 °C from 2,480 m to 2,680 m and the minimum temperature at 2,680 m was above freezing. (2) Elevation had a significant influence on E p; however, the difference in daily E p between 2,480 m and 2,680 m was not significant, which was possibly due to the small difference in elevation between these two sites. (3) VWC had larger range of annual variation at 2,680 m than at 2,480 m, especially for the surface soil layer.We conclude that the decrease in temperature does not effectively explain the sharp transition between these forest types. During the dry season, plants growing at 2,680 m are likely to experience more drought stress. In seeking to understand the mountain forest distribution, further studies should consider the effects of drought stress alongside those of altitude.