Water-induced formation of an alkali-ion dimer in cryptomelane nanorods

Tunneled metal oxides such as α-Mn₈O₁₆ (hollandite) have proven to be compelling candidates for charge-storage materials in high-density batteries. In particular, the tunnels can support one-dimensional chains of K⁺ ions (which act as structure-stabilizing dopants) and H₂O molecules, as these chains are favored by strong H-bonds and electrostatic interactions. In this work, we examine the role of water molecules in enhancing the stability of K⁺-doped α-Mn₈O₁₆ (cryptomelane). The combined experimental and theoretical analyses show that for high enough concentrations of water and tunnel-ions, H₂O displaces K⁺ ions from their natural binding sites. This displacement becomes energetically favorable due to the formation of K²⁺ dimers, thereby modifying the stoichiometric charge of the system. These findings have potentially significant technological implications for the consideration of cryptomelane as a Li⁺/Na⁺ battery electrode. Our work establishes the functional role of water in altering the energetics and structural properties of cryptomelane, an observation that has frequently been overlooked in previous studies.

Water displaces potassium ions and initiates the formation of a homonuclear dimer ion (K²⁺) in the tunnels of hollandite.     

What is the role of acid–acid interactions in asymmetric phosphoric acid organocatalysis? A detailed mechanistic study using interlocked and non-interlocked catalysts

Organocatalysis has revolutionized asymmetric synthesis. However, the supramolecular interactions of organocatalysts in solution are often neglected, although the formation of catalyst aggregates can have a strong impact on the catalytic reaction. For phosphoric acid based organocatalysts, we have now established that catalyst–catalyst interactions can be suppressed by using macrocyclic catalysts, which react predominantly in a monomeric fashion, while they can be favored by integration into a bifunctional catenane, which reacts mainly as phosphoric acid dimers. For acyclic phosphoric acids, we found a strongly concentration dependent behavior, involving both monomeric and dimeric catalytic pathways. Based on a detailed experimental analysis, DFT-calculations and direct NMR-based observation of the catalyst aggregates, we could demonstrate that intermolecular acid–acid interactions have a drastic influence on the reaction rate and stereoselectivity of asymmetric transfer-hydrogenation catalyzed by chiral phosphoric acids.

Supramolecular acid–acid interactions lead to competing monomeric and dimeric pathways in phosphoric acid catalysis – so that stereoselectivities depend on catalyst concentration.     

Persistent Room Temperature Phosphorescence from Triarylboranes: A Combined Experimental and Theoretical Study

Achieving highly efficient phosphorescence in purely organic luminophors at room temperature remains a major challenge due to slow intersystem crossing (ISC) rates in combination with effective non‐radiative processes in those systems. Most room temperature phosphorescent (RTP) organic materials have O‐ or N‐lone pairs leading to low lying (n, π*) and (π, π*) excited states which accelerate k_isc through El‐Sayed's rule. Herein, we report the first persistent RTP with lifetimes up to 0.5 s from simple triarylboranes which have no lone pairs. RTP is only observed in the crystalline state and in highly doped PMMA films which are indicative of aggregation induced emission (AIE). Detailed crystal structure analysis suggested that intermolecular interactions are important for efficient RTP. Furthermore, photophysical studies of the isolated molecules in a frozen glass, in combination with DFT/MRCI calculations, show that (σ, B p)→(π, B p) transitions accelerate the ISC process. This work provides a new approach for the design of RTP materials without (n, π*) transitions.     

激光惯性约束聚变靶制备技术研究进展

在实验室实现聚变反应释放的能量大于点燃聚变反应所需能量的阈值是当今世界ICF研究的主要目标,实现这一目标仍需要深入研究一系列的关键物理问题。在ICF研究中,制靶能力的发展与提升至关重要,靶的质量是实验成功的核心要素之一。本文介绍了国际ICF靶制备工作近年来在新型烧蚀层材料靶丸、新型靶丸支撑技术、优化黑腔材料与构型以及减小燃料填充管直径等方面取得的一系列进展,并结合ICF物理需求,简要阐述了ICF靶的发展趋势。     

A periodic DFT study on adsorption of small molecules(CH4,CO,H2O,H2S,NH3)on the WO3(001) surface-supported Au

Gas molecules(such as CH4,CO,H2O,H2S,NH_3)adsorption on the pure and Au-doped WO3(001)surface have been studied by Density functional theory calculations with generalized gradient approximation.Based on the the calculation of adsorption energy,we found the most stable adsorption site for gas molecules by comparing the adsorption energies of different gas molecules on the WO3(001)surface.We have also compared the adsorption energy of five different gas molecules on the WO3(001)surface,our calculation results show that when the five kinds of gases are adsorbed on the pure WO3(001)surface,the order of the surface adsorption energy is CO>H2S>CH4>H2O>NH3.And the results show that NH3 is the most easily adsorbed gas among the other four gases adsorbed on the surface of pure WO3(001)surface.We also calculated the five different gases on the Au-doped WO3(001)surface.The order of adsorption energy was found to be different from the previous calculation:CO>CH4>H2S>H2O>NH3.These results provide a new route for the potential applications of Au-doped WO3 in gas molecules adsorption.     

大规模合成具有氧空位的多孔Bi2O3用于有效降解亚甲基蓝

光催化降解有机污染物由于其具有低能耗和绿色环保的特点，已经成为研究的热点. 氧化铋纳米晶体的带隙在2.0∽2.8 eV之间，利用它催化可见光降解有机污染物具有较高的活性，从而引起了越来越多的关注. 尽管近年来已经开发了几种制备Bi₂O₃基半导体材料的方法，但是仍然难以用简单的方法大规模地制备高活性的Bi₂O₃催化剂. 因此，开发简单可行的大规模制备Bi₂O₃纳米晶体的方法对于工业废水处理的潜在应用具有重要意义. 本文通过蚀刻商用BiSn粉末，然后进行热处理，成功地大规模制备了多孔Bi₂O₃. 获得的多孔Bi₂O₃在亚甲基蓝(MB)的光催化降解中表现出优异的活性和稳定性. 对该机理的进一步研究表明，多孔Bi₂O₃合适的能带结构允许生成活性氧物种，例如O₂^-·和·OH，可有效降解MB.     

OH+C2H3F的反应机理及产物支化比反应的理论研究

本文对HOC₂H₃F可能解离通道的势能面进行从头算CCSD(T)/CBS//B3LYP/6-311G(d，p)计算，同时对速率常数进行Rice-Ramsperger-Kassel-Marcus计算. 生成主要产物CH₂CHO+HF最有利的反应途径是OHC₂H₃F→i2→TS14→i6→TS9→i3→TS3→CH₂CHO+HF，其中速率决定步骤是HF通过TS11从CO桥接位置解离，能量比反应物高3.8 kcal/mol. 借助中间态TS14，F原子从C_α迁移到C_β位置生成CH₂O+CH₂F，然后通过中间态TS16，H从O迁移到C_α位置；通过中间态TS5，C-C键断裂生成产物，其能量比反应物低1.8 kcal/mol，比TS11低4.0 kcal/mol.     

100kV直流高温超导电缆终端应力锥设计

本文提出了一种新的单直线应力锥设计方法,根据PPLP材料的绝缘特性,结合超导电缆的本体尺寸和设计电压,给出了增饶绝缘厚度和应力锥轴向长度的设计数据,其中增饶绝缘厚度为3.5 mm,应力锥轴向长度为38.5 mm,并对单直线应力锥进行电场数值分析,结果表明,所设计的单直线应力锥满足100 kV直流高温超导电缆运行要求。     

Chiral cyclic [n]spirobifluorenylenes: carbon nanorings consisting of helically arranged quaterphenyl rods illustrating partial units of woven patterns

Chiral cyclic [n]spirobifluorenylenes consisting of helically arranged quaterphenyl rods, illustrating partial units of woven patterns, were designed and synthesized as a new family of carbon nanorings. The synthesis was accomplished by the Ni(0)-mediated Yamamoto-coupling of chiral spirobifluorene building blocks. The structures of the cyclic 3-, 4-, and 5-mers were determined by X-ray crystallographic analysis. These carbon nanorings exhibited a strong violet colored emission with high quantum yields in solution (95%, 93%, and 94% for 3-, 4-, and 5-mer, respectively). Other spectroscopic properties, including their chiroptical properties, were also investigated. The g-values for circularly polarized luminescence were found to be in the order of 10⁻³. Characteristic spiroconjugation induced by multiple (≧3) bifluorenyl units, for example the even-odd effect of the number of units in the matching of the signs of the orbitals, was also indicated by DFT calculations.

Chiral cyclic [n]spirobifluorenylenes consisting of helically arranged quaterphenyl rods, illustrating partial units of woven patterns, were designed and synthesized as a new family of carbon nanorings.