Surface Oxygen Coordination of Hydrogen Bond Chemistry for Aqueous Ammonium Ion Hybrid Supercapacitor

Aqueous ammonium ion hybrid supercapacitor (A-HSC) combines the charge storage mechanisms of surface adsorption and bulk intercalation, making it a low-cost, safe, and sustainable energy storage candidate. However, its development is hindered by the low capacity and unclear charge storage fundamentals. Here, the strategy of phosphate ion-assisted surface functionalization is used to increase the ammonium ion storage capacity of an α-MoO₃ electrode. Moreover, the understanding of charge storage mechanisms via structural characterization, electrochemical analysis, and theoretical calculation is advanced. It is shown that NH₄⁺ intercalation into layered α-MoO₃ is not dominant in the A-HSC system; rather, the charge storage mainly depends on the adsorption energy of surface “O” to NH₄⁺. It is further revealed that the hydrogen bond chemistry of the coordination between “O” of surface phosphate ion and NH₄⁺ is the reason for the capacity increase of MoO₃. This study not only advances the basic understanding of rechargeable aqueous A-HSC but also demonstrates the promising future of surface engineering strategies for energy storage devices.     

Carbon Black-Supported Single-Atom Co?N?C as an Efficient Oxygen Reduction Electrocatalyst for H2O2 Production in Acidic Media and Microbial Fuel Cell in Neutral Media

Single metal atom isolated in nitrogen-doped carbon materials (M N C) are effective electrocatalysts for oxygen reduction reaction (ORR), which produces H₂O₂ or H₂O via 2-electron or 4-electron process. However, most of M N C catalysts can only present high selectivity for one product, and the selectivity is usually regulated by complicated structure design. Herein, a carbon black-supported Co N C catalyst (CB@Co N C) is synthesized. Tunable 2-electron/4-electron behavior is realized on CB@Co-N-C by utilizing its H₂O₂ yield dependence on electrolyte pH and catalyst loading. In acidic media with low catalyst loading, CB@Co N C presents excellent mass activity and high selectivity for H₂O₂ production. In flow cell with gas diffusion electrode, a H₂O₂ production rate of 5.04 mol h⁻¹ g⁻¹ is achieved by CB@Co N C on electrolyte circulation mode, and a long-term H₂O₂ production of 200 h is demonstrated on electrolyte non-circulation mode. Meanwhile, CB@Co N C exhibits a dominant 4-electron ORR pathway with high activity and durability in pH neutral media with high catalyst loading. The microbial fuel cell using CB@Co N C as the cathode catalyst shows a peak power density close to that of benchmark Pt/C catalyst.     

甲烷掺混氢气的燃烧特性试验研究

通过在定容燃烧室内研究不同的初始温度、初始压力、燃空当量比、掺氢比下甲烷-氢气-空气混合气的燃烧压力变化规律,得到了上述条件对混合气最大燃烧压力、最大压力升高率、火焰发展期、燃烧持续期以及最大燃烧压力循环变动的影响.研究结果表明:其他初始条件不变时,甲烷-氢气-空气混合气在高温低压时火焰传播的更快;随着甲烷中掺氢比增加...     

氢对TA16钛合金性能影响研究

研究氢对TA16钛合金显微组织、氢脆行为和应力腐蚀行为的影响,以及TA16钛合金在8.5 MPa高温碱性水中的吸氢性能。结果表明,氢在TA16钛合金中形成面心立方的δ相氢化物TiHx(x=1~2)。在室温条件下,TA16钛合金氢脆敏感性随着合金中的氢含量的增加而增大;在8.5 MPa高温碱性水中,TA16钛合金的应力腐蚀敏感性随着合金中氢含量的增加而增大,但合金中氢的体积浓度小于350 mL/m3时,合金的应力腐蚀敏感指数小于0.2。在8.5 MPa高温碱性水中,TA16钛合金的吸氢量随着浸泡时间的增加而增大,浸泡13 000 h后,TA16钛合金的吸氢体积浓度小于50 mL/m3,合金表面形成的由TiO、TiO2和Ti2O3组成的致密氧化膜。     

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。