LaNi5及其氢化物的价电子结构理论计算

运用固体与分子经验电子理论(EET),定量分析LaNi5溶氢前后的价电子结构变化。结果表明:LaNi5中,平行于xoy平面内原子间的键合较强,而平行于z轴方向原子间的键合很弱,原子键合呈现明显的各向异性分布。LaNi5H7中,Ni—H键的键能远大于La—H键,正是通过这两种元素的协调作用,形成中等强度的化学键,有利于可逆的吸放氢反应发生。EET理论给出的电子结构计算结果与第一原理的计算结果相吻。LaNi5溶氢后,平均晶格电子数显著减少,脆性增加,同时考虑到LaNi5中原子键合的各向异性分布,因此该合金反复吸放氢后易粉化。     

Transfer Hydrogenation in Mesoporous Palladium: Polar Hydrogen Engineering to Realize High Selectivity of Alkyne Semi-Hydrogenation

Semi-hydrogenation of alkynes to industrially important alkenes is earnestly desirable in the fine chemical industry but energetically unfavorable. Herein, it is reported that mesoporous palladium (meso-Pd) catalyst changes the hydrogenation pathways in ethanol with ammonium borane as the hydrogen source, realizing the high catalytic selectivity of ≈99% in semi-hydrogenation of alkynes. Mechanism studies reveal that the active polar hydrogen can be produced and reserved well in the electron-rich mesoporous channels of meso-Pd catalyst, resulting in a transfer hydrogenation pathway, which selectively semi-hydrogenates alkynes into alkenes without over-hydrogenating alkenes into alkanes. Moreover, it is demonstrated that the polar hydrogen engineering of meso-Pd catalyst is highly efficient in various alkyne semi-hydrogenation and chemoselective hydrogenation reactions. The results thus establish metal catalyst mesostructuring as an alternative route for engineering polar hydrogen in the transfer hydrogenation reactions, thus realizing the high catalytic selectivity in various selective catalysis.     

Metal Single-Atom Cocatalyst on Carbon Nitride for the Photocatalytic Hydrogen Evolution Reaction: Effects of Metal Species

Single-atom (SA) catalysts exhibit high activity in various reactions because there are no inactive internal atoms. Accordingly, SA cocatalysts are also an active research fields regarding photocatalytic hydrogen (H₂) evolution which can be generated by abundant water and sunlight. Herein, it is investigated whether 10 transition metal elements can work as an SA on graphitic carbon nitride (g-C₃N₄; i.e., gCN), a promising visible-light-driven photocatalyst. A method is established to prepare SA-loaded gCN at high loadings (weight of ≈3 wt.% for Cu, Ni, Pd, Pt, Rh, and Ru) by modulating the photoreduction power. Regarding Au and Ag, SAs are formed with difficulty without aggregation because of the low binding energy between gCN and the SA. An evaluation of the photocatalytic H₂-evolution activity of the prepared metal SA-loaded gCN reveals that Pd, Pt, and Rh SA-loaded gCN exhibits relatively high H₂-evolution efficiency per SA. Transient absorption spectroscopy and electrochemical measurements reveal the following: i) Pd SA-loaded gCN exhibits a particularly suitable electronic structure for proton adsorption and ii) therefore they exhibit the highest H₂-evolution efficiency per SA than other metal SA-loaded gCN. Finally, the 8.6 times higher H₂-evolution rate per active site of Pd SA is achieved than that of Pd-nanoparticles cocatalyst.     

Effect of hydrogen annealing on hot-carrier instability of X-Ray irradiated CMOS devices

In the very large scale integration (VLSI) technology, the need for high density and high performance integrated circuit (IC) chip demands advanced processing techniques that often result in the generation of high energy particles and photons. Frequently, the radiation damage are introduced by these energetic particles and photons during device processing. The radiation damage created by x-ray irradiation, which can often occur during metal sputtering process, has been shown to potentially enhance hot-carrier instability if the neutral traps which act as electron or hole traps in the silicon dioxide is not annealed out. In this paper, we investigate the effects of annealing using different hydrogen contents and temperatures on the device characteristics and hot carrier instability of 0.5 μm CMOS devices after 1500 mJ/cm² synchrotron x-ray irradiation. Three different annealing conditions were employed; 400° C H₂, 450° C H₂, and 400° C H₂ + N₂. It is found that for all three different hydrogen anneals the normal characteristics of irradiated CMOS devices can be effectively recovered. The hot-carrier instability of bothp- andn-channel MOSFETs are significantly enhanced after x-ray irradiation due to the creation of neutral traps and positively charged oxide traps. After high H₂ (100%) concentration anneals at 450° C, the hot-carrier instability in irradiatedn-channel devices is greatly reduced and comparable to the non-irradiated devices. Although the hot-carrier instability inp-channel devices is also significantly reduced after annealing, the threshold voltage shifts are still enhanced as compared to the devices without exposure to x-ray irradiation during maximum gate current stress. For those non-irradiated, but hydrogen-annealedp-channel devices, the hot-carrier instability was observed to be worse than the non-irradiated device without hydrogen annealing.     

Effects of hydrogen annealing on MOS oxides

The effects of annealing MOS oxides at high temperatures in hydrogen or deuterium have been studied. Annealing at temperatures above ≈800° C causes a dramatic increase in the radiation sensitivity of the oxide. High temperature annealing also appears to cause a decrease in the dielectric strength of the oxide. Secondary ion mass spectrometry (SIMS) profiles of deuterium-annealed oxides reveal a substantial uptake of deuterium during the annealing. These results suggest that exposure of gate oxides to hydrogen at high temperatures should be avoided.     

国内正在崛起的新型电池

我国电池产量居世界首位, 但其中产量的９０％ 以上为低档次电池。近１０多年来, 我国新型电池的生产引人注目。其中有碱性锌锰电池、锂一次电池及小型可充电镉镍电池、氢镍电池和锂离子电池。介绍了国内正在崛起的几种新型电池。     

Modulation of Electron Structure and Dehydrogenation Kinetics of Nickel Phosphide for Hydrazine-Assisted Self-Powered Hydrogen Production in Seawater

The electrocatalytic production of hydrogen from seawater provides a low-cost way to realize energy conversion, but is restricted by high potential for seawater electrolysis and the chlorine oxidation reaction (ClOR) at the anode. Here, the self-growth of Mo-doped Ni₂P nanosheet arrays with rich P vacancies on molybdenum-nickel foam (MNF) (Mo-Ni₂P_v@MNF) is reported as bifunctional catalyst for Cl-free hydrogen production by coupling hydrogen evolution reaction (HER) with hydrazine oxidation reaction (HzOR) in seawater. Impressively, the Mo-Ni₂P_v@MNF electrode as bifunctional catalyst has an excellent activity for overall hydrazine splitting (OHzS) with an ultralow voltage of only 571 mV at 1000 mA cm⁻² and can maintain stability for an ultra-long time of 1000 h at 100 mA cm⁻². Moreover, integration of OHzS into self-assembled hydrazine fuel cells (DHzFC) or solar cells can enable the self-powered H₂ production. The industrial hydrazine sewage as feed for the above eletrolysis system can be degraded to ≈5 ppb rapidly. Density functional thoery calculations demonstrate that the electronic structure modulation induced by P vacancies and Mo doping can not only achieve thermoneutral ΔG_H* for hydrogen evolution reaction but also enhance dehydrogenation kinetics from *N₂H₄ to *NHNH₂ for HzOR, achieving enhanced dehydrogenation kinetics.     

Hydrogen‐Bonded Organic Semiconductors as Stable Photoelectrocatalysts for Efficient Hydrogen Peroxide Photosynthesis

Research on semiconductor photocatalysts for the conversion of solar energy into chemical fuels has been at the forefront of renewable energy technologies. Water splitting to produce H₂ and CO₂ reduction to hydrocarbons are the two prominent approaches. A lesser‐known process, the conversion of solar energy into the versatile high‐energy product H₂O₂ via reduction of O₂ has been proposed as an alternative concept. Semiconductor photoelectrodes for the direct photosynthesis of H₂O₂ from O₂ have not been applied up to now. Photoelectrocatalytic oxygen reduction to peroxides in aqueous electrolytes by hydrogen‐bonded organic semiconductor is observed photoelectrodes. These materials have been found to be remarkably stable operating in a photoelectrochemical cell converting light into H₂O₂ under constant illumination for at least several days, functioning in a pH range from 1 to 12. This is the first report of a semiconductor photoelectrode for H₂O₂ production, with catalytic performance exceeding prior reports on photocatalysts by one to two orders of magnitude in terms of peroxide yield/catalyst amount/time. The combination of a strongly reducing conduction band energy level with stability in aqueous electrolytes opens new avenues for this widely available materials class in the field of photo(electro) catalysis.     

ZnO nanonails: Organometallic synthesis,self-assembly and enhanced hydrogen gas production

We report the rational synthesis and characterizations of defect-rich zinc oxide (ZnO) nanonails that were prepared by organometallic approach and their implementation as an efficient photocatalyst for hydrogen (H₂) generation. The ZnO nanonails were prepared from zinc stearate in n-octadecene that serves as non-coordinating solvent without the presence of any capping agent. Transmission electron microscopy (TEM) studies reveal that the individual triangular prismatic nanonail has an average edge length of 50–70 nm and it appears to have preferred growth orientation along [0001] crystal axis. Intriguingly, this nanonails show oriented-attachment along the flat-basal edge and self-assembled into twinned structure. Such structure is interconnected via a narrow-gap to form symmetrical twinned-like nanonails with truncated tips at both ends. In comparison to ZnO commercial nanopowder, ZnO nanonails show significant enhancement in photocatalytic H₂ gas generation rate of 53.33% under UV light for 5 h. These results demonstrate ZnO nanonails to be a substantial potential photocatalyst for efficient photocatalytic applications.